CN102037086B - Epoxy resin reactive diluent compositions - Google Patents

Epoxy resin reactive diluent compositions Download PDF

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Publication number
CN102037086B
CN102037086B CN2009801185303A CN200980118530A CN102037086B CN 102037086 B CN102037086 B CN 102037086B CN 2009801185303 A CN2009801185303 A CN 2009801185303A CN 200980118530 A CN200980118530 A CN 200980118530A CN 102037086 B CN102037086 B CN 102037086B
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cyclohexanedimethanol
epoxy resin
cis
weight
epoxy
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CN102037086A (en
Inventor
罗伯特·E·小赫夫纳
小赫尔
詹姆斯·W·林格
约翰·N·阿伊罗普洛斯
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Blue Cube Intellectual Property Co ltd
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Dow Global Technologies LLC
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/226—Mixtures of di-epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Abstract

An epoxy resin reactive diluent composition comprises an epoxy resin diluent (A) and a resin compound (B), wherein the epoxy resin diluent (A) comprises a cis, trans-1,3- and -1,4-cyclohexanedimethylether moiety; and wherein the resin compound (B) comprises one or more epoxy resins other than the epoxy resin diluent (A). A curable epoxy resin composition comprises the epoxy resin reactive diluent composition and a curing agent and/or curing catalyst therefore. A cured epoxy resin is prepared by curing the curable epoxy resin composition.

Description

Resins, epoxy reactive diluent composition
Background of invention
Invention field
The present invention relates to comprise cis, anti-form-1,3-and-1, the Resins, epoxy reactive diluent composition of 4-hexanaphthene dimethyl ether part, with the curable epoxy that comprises described Resins, epoxy reactive diluent composition, and the cured epoxy resin reactive diluent composition that passes through the method preparation of the described curable epoxy resin composition of curing.
Background and description of Related Art
Conventional Resins, epoxy reactive diluent and preparation thereof are as known in the art, and for example are described in McGraw Hill by New York by Henry Lee and Kris Neville, the Resins, epoxy handbook that Inc. publishes ( Handbook of Epoxy Resins)On (1967) 13-9 to the 13-18 pages or leaves (1967).
Yet instruction does not comprise cis, anti-form-1 in the prior art, 3-and-1, the open or hint of the Resins, epoxy reactive diluent composition of 4-hexanaphthene dimethyl ether part.There is not instruction to comprise the open or hint of the cured epoxy resin reactive diluent composition of the curable epoxy of described Resins, epoxy reactive diluent composition and the method preparation by solidifying described curable epoxy resin composition in the prior art yet.
Summary of the invention
The present invention uses and comprises cis, anti-form-1,3-and-1, the Resins, epoxy of 4-hexanaphthene dimethyl ether part reacts with preparation Resins, epoxy reactive diluent composition with conventional Resins, epoxy (for example, the diglycidylether of dihydroxyphenyl propane) as the Resins, epoxy reactive diluent.Resulting Resins, epoxy reactive diluent composition can with solidifying agent and/or catalyzer blend to form curable epoxy resin composition.By curable epoxy resin composition is solidified, can obtain cured epoxy resin.
One aspect of the present invention relates to a kind of Resins, epoxy reactive diluent composition that comprises epoxy resin diluent (A) and resin compound (B), wherein said epoxy resin diluent (A) comprises cis, anti-form-1,3-and-1,4-hexanaphthene dimethyl ether part, and wherein said resin compound (B) comprises the Resins, epoxy that one or more are different from epoxy resin diluent (A).
Another aspect of the present invention relates to a kind of curable epoxy resin composition that comprises above-mentioned Resins, epoxy reactive diluent composition.
Another aspect of the present invention relates to a kind of cured epoxy resin for preparing by the method for solidifying described curable epoxy resin composition.
Detailed Description Of The Invention
In the following detailed description, in conjunction with its preferred embodiment specific embodiments of the present invention is described.Yet specific to the specific embodiments of present technique or concrete purposes, it is intended to only be exemplary and accurate description that example embodiment only is provided with regard to following description.Therefore, the invention is not restricted to specific embodiments described below, but; The present invention includes all alternativess, variation and equivalent in the true scope that falls into appended claim.
Unless otherwise indicated, mentioning of material, compound or component comprised this material, compound or component self, and with the combination of other material, compound or component, for example mixture of compound or combination.
As used in this article, singulative " (a) ", " one (an) " and " described (the) " comprise plural reference, unless context is clearly stipulated in addition.
The invention provides a kind of Resins, epoxy reactive diluent composition, it comprises epoxy resin diluent (A) and resin compound (B), and wherein said epoxy resin diluent (A) comprises cis, anti-form-1,3-and-1,4-hexanaphthene dimethyl ether part; And wherein said resin compound (B) comprises the Resins, epoxy that one or more are different from epoxy resin diluent (A).
Term " reactive diluent " refers to add in material or the compound (for example, Resins, epoxy) as used herein, comprises the thinner that for example reduces viscosity with the character that changes described material or compound.
As used herein, term " cis, anti-form-1,3-and-1,4-hexanaphthene dimethyl ether part " is illustrated in and comprises four kinds of geometrical isomers in the Resins, epoxy, it is cis-1,3-hexanaphthene dimethyl ether, anti-form-1,3-hexanaphthene dimethyl ether, cis-1,4-hexanaphthene dimethyl ether, and anti-form-1, the structure of 4-hexanaphthene dimethyl ether or the blend of chemical structure.Four kinds of geometrical isomers are shown by following array structure:
Usually, epoxy resin diluent of the present invention (A) is by comprising method (for example, the epoxidation processes) preparation that makes following substance reaction: (a) cis-1, the 3-cyclohexanedimethanol, anti-form-1,3-cyclohexanedimethanol, cis-1, the 4-cyclohexanedimethanol, and anti-form-1, the mixture of 4-cyclohexanedimethanol (is also referred to as cis-1,3-and 1, the 4-cyclohexanedimethanol) with (b) epihalohydrin and (c) alkaline working substance.Described method can randomly comprise, (d) solvent and/or (e) catalyzer.Described method can for, for example, slurries epoxidizing method, anhydrous epoxidizing method, or the coupling of Louis acid catalysis and epoxidizing method.
Cis, anti-form-1 for the preparation of epoxy resin diluent of the present invention (A), 3-and 1, the mixture of 4-cyclohexanedimethanol can comprise cis, the anti-form-1 of manipulated variable, the 3-cyclohexanedimethanol, for example, based on the gross weight of mixture, about 1 weight % is to about 99 weight %, preferred about 15 weight % are to about 85 weight %, and more preferably from about 40 weight % are to cis, the anti-form-1 of about 60 weight %, 3-cyclohexanedimethanol.
Comprise cis, anti-form-1,3-and-1, the Resins, epoxy of 4-hexanaphthene dimethyl ether part and for the preparation of its detailed description of method be provided at the u.s. patent application serial number of common pending trial _ _ _ _ _ _ _ (attorney 64833) in, this U.S. Patent application is combined in this by reference.
Have been found that, as the u.s. patent application serial number of common pending trial _ _ _ _ _ _ disclosed in (attorney 64833), comprise cis, anti-form-1,3-and-1, the Resins, epoxy of 4-hexanaphthene dimethyl ether part has the character of improvement, as do not have in room temperature crystallization and with only comprise cis, trans 1, the Resins, epoxy of the 4-hexanaphthene dimethyl ether part low viscosity of comparing.The character of these improvement has improved the ability that Resins, epoxy is accepted high solid content.In addition, as discloseder cis, the anti-form-1 of comprising in the patent application of above-mentioned common pending trial, 3-and-1, the Resins, epoxy of 4-hexanaphthene dimethyl ether part has low-down muriate and (comprises ion, hydrolyzable and total muriate) content and high 2-glycidyl ether content, this provides raising and reactivity conventional epoxy curing agent to Resins, epoxy, the potential corrosion of reduction and the electrical property that improves.
Epoxy resin diluent of the present invention (A) comprises cis, anti-form-1,3-and-1,4-hexanaphthene dimethyl ether part.Preferably, epoxy resin diluent (A) comprises a kind of in the following Resins, epoxy:
(1) Resins, epoxy, it comprises cis-1, the diglycidylether of 3-cyclohexanedimethanol, anti-form-1, the diglycidylether of 3-cyclohexanedimethanol, cis-1, the diglycidylether of 4-cyclohexanedimethanol, and anti-form-1, the diglycidylether of 4-cyclohexanedimethanol (is also referred to as cis, anti-form-1, the diglycidylether of 3-and 1,4 cyclohexane dimethanol);
(2) Resins, epoxy, it comprises cis-1, the diglycidylether of 3-cyclohexanedimethanol, anti-form-1, the diglycidylether of 3-cyclohexanedimethanol, cis-1, the diglycidylether of 4-cyclohexanedimethanol, anti-form-1, the diglycidylether of 4-cyclohexanedimethanol and their one or more oligopolymer;
(3) Resins, epoxy, it comprises cis-1, the diglycidylether of 3-cyclohexanedimethanol, anti-form-1, the diglycidylether of 3-cyclohexanedimethanol, the diglycidylether of cis-1,4 cyclohexane dimethanol, anti-form-1, the diglycidylether of 4-cyclohexanedimethanol, cis-1, the monoglycidyl ether of 3-cyclohexanedimethanol, anti-form-1, the monoglycidyl ether of 3-cyclohexanedimethanol, the monoglycidyl ether of cis-1,4 cyclohexane dimethanol, and anti-form-1, the monoglycidyl ether of 4-cyclohexanedimethanol; Or
(4) Resins, epoxy, it comprises cis-1, the diglycidylether of 3-cyclohexanedimethanol, anti-form-1, the diglycidylether of 3-cyclohexanedimethanol, cis-1, the diglycidylether of 4-cyclohexanedimethanol, anti-form-1, the diglycidylether of 4-cyclohexanedimethanol, cis-1, the monoglycidyl ether of 3-cyclohexanedimethanol, anti-form-1, the monoglycidyl ether of 3-cyclohexanedimethanol, cis-1, the monoglycidyl ether of 4-cyclohexanedimethanol, anti-form-1, the monoglycidyl ether of 4-cyclohexanedimethanol and their one or more oligopolymer.
Above-mentioned Resins, epoxy (3) and (4) can comprise the cis-1 of manipulated variable, the monoglycidyl ether of 3-cyclohexanedimethanol, anti-form-1, the monoglycidyl ether of 3-cyclohexanedimethanol, the monoglycidyl ether of cis-1,4 cyclohexane dimethanol, and anti-form-1, the monoglycidyl ether of 4-cyclohexanedimethanol (being also referred to as cis, anti-form-1, single diglycidylether of 3-and 1,4 cyclohexane dimethanol).For example, based on the gross weight of epoxy resin diluent (A), the amount of monoglycidyl ether can be at about 0.1 weight % to the scope of about 90 weight %; Preferably, at about 0.1 weight % to the scope of about 20 weight %; And more preferably, at about 0.1 weight % to the scope of about 10 weight %.
Resin compound of the present invention (B) comprises the Resins, epoxy that one or more are different from epoxy resin diluent (A).The Resins, epoxy that can be used as resin compound (B) can be any compound that contains epoxy group(ing), and its each molecule has on average more than an epoxy group(ing).Epoxy group(ing) can be connected on any oxygen, sulphur or the nitrogen-atoms, or the Sauerstoffatom that singly-bound closes be connected to-carbon atom on the CO-O-group on.Oxygen, sulphur, nitrogen-atoms, or-carbon atom of CO-O-group can be connected on aliphatic series, alicyclic, many cyclic aliphatics or the aromatic hydrocarbyl.Aliphatic, alicyclic, many cyclic aliphatic or aromatic hydrocarbyl can be replaced by any inert substituent, and described inert substituent includes but not limited to, halogen atom, preferred fluorine, bromine or chlorine; Nitro; Or group can be connected to and contains on average more than 1-(O-CHR a-CHR a) tOn the terminal carbon of the compound of-group, each R wherein aIndependently for hydrogen atom or contain alkyl or the halogenated alkyl group of 1 to 2 carbon atom, condition is R only aGroup can be haloalkyl, and t has 1 to about 100, preferred 1 to about 20, and more preferably 1 to about 10, most preferably 1 to about 5 value.
The more specifically example that is applicable to the Resins, epoxy of resin compound (B) comprises: following diglycidylether: 1,2-dihydroxy-benzene (pyrocatechol); 1,3-dihydroxy-benzene (Resorcinol), 1,4-dihydroxy-benzene (quinhydrones), 4,4 '-isopropylidene biphenol (dihydroxyphenyl propane), 4,4 '-dihydroxyl ditan, 3,3 ', 5,5 '-tetrabromo-bisphenol, 4,4 '-sulfo-biphenol; 4,4 '-alkylsulfonyl biphenol; 2,2 '-the alkylsulfonyl biphenol; 4,4 '-dihydroxyl phenylbenzene oxidation thing; 4,4 '-dihydroxy benaophenonel; 1,1 '-two (4-hydroxy phenyl)-1-diphenylphosphino ethanes; 3,3 '-5,5 '-tetrachlorobisphenol A; 3,3 '-dimethoxy dihydroxyphenyl propane; 4,4 '-dihydroxybiphenyl; 4,4 '-dihydroxyl-Alpha-Methyl stilbene; 4,4 '-dihydroxy-benzene formylaniline; 4,4 '-dihydroxyl stilbene; 4,4 '-dihydroxyl-alpha-cyano stilbene; N, N '-two (4-hydroxy phenyl) terephthalamide; 4,4 '-dihydroxyl nitrogen benzide; 4,4 '-dihydroxyl-2,2 '-dimethyl oxidation azo-group benzene; 4,4 '-the dihydroxyl dibenzenyl; 4,4 '-the dihydroxyl phenyl styryl ketone; 4-hydroxy phenyl-4-hydroxybenzoate; Dipropylene glycol, 1,4-butyleneglycol, neopentyl glycol, poly-(propylene glycol), thiodiglycol; The triglycidyl ether of three (hydroxy phenyl) methane; The polyglycidyl ether of phenol-aldehydic acid catalyzing and condensing product (novolac resin) that phenol or alkyl or halogen replace; Four following glycidyl amines: 4,4 '-diaminodiphenyl-methane; 4,4 '-the diamino stilbene; N, N '-dimethyl-4,4 '-diamino stilbene; 4,4 '-the diaminobenzene formylaniline; 4,4 '-benzidine; The polyglycidyl ether of the condensation product of the phenol that Dicyclopentadiene (DCPD) or its oligopolymer and phenol or alkyl or halogen replace; With their any combination.
The Resins, epoxy that can be used as resin compound (B) can also comprise advanced (advanced) epoxy resin product.Advanced Resins, epoxy can be Resins, epoxy and aromatics contain two and the advanced person of poly-hydroxy or carboxylic acid cpd react the product of (advancement reaction).The Resins, epoxy that in advanced person reaction, uses can comprise above-mentioned be applicable to comprise two or the Resins, epoxy of the resin compound (B) of polyglycidyl ether in any or multiple.
Aromatics contain two and the examples for compounds of poly-hydroxy or carboxylic acid comprise quinhydrones, Resorcinol, pyrocatechol, 2,4-dimethyl Resorcinol; The 4-chloro resorcinol; Duroquinol; Dihydroxyphenyl propane; 4,4 '-the dihydroxyl ditan; 4,4 '-the sulfo-biphenol; 4,4 '-the alkylsulfonyl biphenol; 2,2 '-the alkylsulfonyl biphenol; 4,4 '-dihydroxyl phenylbenzene oxidation thing; 4,4 '-dihydroxy benaophenonel; Two (4-the hydroxy phenyl)-1-diphenylphosphino ethanes of 1,1-; 4,4 '-two (4 (4-hydroxyphenoxy)-phenylsulfone) diphenyl ether; 4,4 '-dihydroxydiphenyl disulfide; 3,3 ', 3,5 '-tetrachloro-4,4 '-the isopropylidene biphenol; 3,3 ', 3,5 '-tetrabromo-4,4 '-the isopropylidene biphenol; 3,3 '-dimethoxy-4 ', 4 '-the isopropylidene biphenol; 4,4 '-dihydroxybiphenyl; 4,4 '-dihydroxyl-Alpha-Methyl stilbene; 4,4 '-the dihydroxy-benzene formylaniline; Two (4-hydroxy phenyl) terephthalate; N, N '-two (4-hydroxy phenyl) terephthalamide; Two (4 '-hydroxy diphenyl) terephthalate; 4,4 '-the dihydroxy phenyl benzoic ether; Two (4 '-hydroxy phenyl)-1,4-benzene diimine; 1,1 '-bis(4-hydroxyphenyl) cyclohexane; Phloroglucinol; Pyrogallol; 2,2 ', 5,5 '-the tetrahydroxy sulfobenzide; Three (hydroxy phenyl) methane; The Dicyclopentadiene (DCPD) biphenol; Three cyclopentadiene biphenol; Terephthalic acid; M-phthalic acid; 4,4 '-the benzanilide dicarboxylic acid; 4,4 '-the phenylbenzoate dicarboxylic acid; 4,4 '-the stilbene dicarboxylic acid; Hexanodioic acid; With their any combination.
The preparation of above-mentioned advanced epoxy resin product can use currently known methods to carry out, for example, Resins, epoxy and one or more each molecules have on average the advanced person's reaction more than the suitable combination thing of 1 hydrogen atoms, wherein hydrogen atoms have with Resins, epoxy in the reactivity of epoxy group(ing).
Equivalents by epoxy group(ing) in the equivalents/Resins, epoxy of hydrogen atoms, each molecule has on average and is generally about 0.01: 1 to about 0.95: 1 more than the compound of 1 hydrogen atoms and the ratio of Resins, epoxy, preferred about 0.05: 1 to about 0.8: 1, more preferably from about 0.10: 1 to about 0.5: 1.
Each molecule has average examples for compounds more than 1 hydrogen atoms and comprises dihydroxy aromatic compounds, dithiol, disulfonic acid amide or dicarboxylic acid compound, or contain a primary amine or amide group, two secondary amine groups, secondary amine group and phenolic hydroxyl group, secondary amine group and hydroxy-acid group or the compound of a phenolic hydroxyl group and a hydroxy-acid group and their any combination.
Advanced reaction can be under the situation that has or do not exist solvent and application of heat and stirring carry out.Advanced reaction can or be lower than the pressure of atmosphere and at about 20 ℃ to about 260 ℃ at atmosphere, super large gas, preferably, about 80 ℃ to about 240 ℃, more preferably from about 100 ℃ extremely about 200 ℃ temperature carry out.
Finishing the advanced person depends on such as following factors the required time of reaction: the temperature of employing, each molecule of employing have the chemical structure more than the Resins, epoxy of the chemical structure of the compound of 1 hydrogen atoms and employing.Comparatively high temps may need the shorter reaction time, and lesser temps may need the long reaction times.
Usually, the time that advanced reaction is finished can be at about 5 minutes to about 24 hours, and preferred about 30 minutes to about 8 hours, more preferably from about 30 minutes extremely in about 4 hours scope.
Catalyzer can also be added in the advanced reaction.The example of catalyzer can comprise phosphine, quaternary ammonium compound,
Figure BPA00001257566000071
Compound and tertiary amine.Catalyzer can with based on about 0.01 weight % of the gross weight of Resins, epoxy to about 3 weight %, preferred about 0.03 weight % is to about 1.5 weight %, more preferably from about 0.05 weight % uses to the amount of about 1.5 weight %.
Be provided at United States Patent (USP) 5,736 about can be used for for the preparation of other details of advanced person's reaction of the advanced epoxy resin product of the resin compound that can adopt in the present invention (B), in 620 and Henry Lee and Kris Neville Resins, epoxy handbook (Handbook of Epoxy Resins)In, this United States Patent (USP) and Resins, epoxy handbook are combined in this by reference.
Preferably by blending epoxy thinner (A) and resin compound (B) preparation, wherein resin compound (B) comprises the Resins, epoxy that one or more are different from epoxy resin diluent (A) to Resins, epoxy reactive diluent composition of the present invention.
Epoxy resin diluent (A) can be joined in the Resins, epoxy reactive diluent composition with the sense equivalent.For example, epoxy resin diluent can be joined in the Resins, epoxy reactive diluent composition with the amount that the scope with viscosity of expecting according to the concrete end-use that is intended to for Resins, epoxy reactive diluent composition will be provided.
The viscosity of expectation is usually by being used for the temperature of cured epoxy resin reactive diluent composition, the final concrete curing catalysts that is used for cured epoxy resin reactive diluent composition and/or solidifying agent and control for the desired final mechanical properties of cured epoxy resin reactive diluent composition.
For example, if with the filler blend of Resins, epoxy reactive diluent composition and significant quantity, then need have than low-viscosity epoxy resin reaction diluent composition usually and more epoxide-reactive thinner (A) should be added Resins, epoxy reactive diluent composition.Yet, if the final mechanical properties of expectation cured epoxy resin diluent composition near the mechanical properties of cured resin compound (B), then uses the epoxide-reactive thinner (A) of minimum to reduce the viscosity of Resins, epoxy reactive diluent composition usually.
Usually, based on the gross weight of epoxide-reactive diluent composition, epoxy resin diluent (A) can be with about 0.5% to about 99%, and preferred about 5% to about 55%, and more preferably from about 10% to about 40% amount is used.
According to the present invention, curable epoxy resin composition comprises (a) Resins, epoxy reactive diluent of the present invention composition, (b) at least a solidifying agent, (c) and/or at least a curing catalysts.
Term " curable " (being also referred to as " thermal curable ") expression composition can experience and will make it reach the condition of curing or thermofixation state or condition.
Term " solidifies " or " thermofixation " existed by L R.Whittington Richard Whittington plastics dictionary (Whittington ' s Dictionary of Plastics)(1968) on the 239th page as give a definition: " be infusibility and insoluble in its final state basically as resin or the plastic compound of finishing goods.Thermosetting resin usually some stage in their preparations or processing be liquid, it is by heating, catalysis or some other chemical means curing.After solidifying fully, thermosetting material can not be softening again by heating.Being generally more thermoplastic plastics can be by becoming thermoset with the crosslinked means of other material.″
The solidifying agent and/or the catalyzer that are used for curable epoxy resin composition can be for cured epoxy resin known any solidifying agent and/or catalyzer.
The example of the solidifying agent of Shi Yonging comprises in the present invention: aliphatic series, and alicyclic, how alicyclic or aromatic primary monoamine; Aliphatic series, alicyclic, how alicyclic or aromatic primary and secondary polyamine; Carboxylic acid and acid anhydride thereof; The aromatics hydroxy-containing compounds; Imidazoles; Guanidine; Urea-formaldehyde resin; The melamine amine-aldehyde resins; The alkoxylate urea-formaldehyde resin; Alkoxylate melamine amine-aldehyde resins; Amido amine; Epoxy resin adduct; With their any combination.
Specially suitable solidifying agent comprises, for example, and methylene-dianiline; 4,4 '-the diamino stilbene; 4,4 '-diamino-Alpha-Methyl stilbene; 4,4 '-the diaminobenzene formylaniline; Dyhard RU 100; Quadrol; Diethylenetriamine; Triethylenetetramine (TETA); Tetren; Urea-formaldehyde resins; Melamine formaldehyde resin; The methylolation urea-formaldehyde resins; The methylolation melamine formaldehyde resin; The P-F novolac resin, cresols-formaldehyde phenolic resin varnish, sulfanilamide (SN), diamino diphenyl sulfone, diethyl toluene diamine; The 4-tert-butyltoluene diamines; The amino hexahydroaniline of two-4-; Isophorone diamine; Diamino-cyclohexane; Hexamethylene-diamine; Piperazine; Aminoethylpiperazine; 2,5-dimethyl-2, the 5-hexanediamine; 1,12-dodecane diamines; The amino propylamine of three-3-; With their any combination.
The example of suitable curing catalysts comprises: boron trifluoride, boron fluoride etherate, aluminum chloride; iron(ic) chloride, zinc chloride, silicon tetrachloride; tin chloride, titanium tetrachloride, butter of antimony; boron trifluoride monoethanolamine title complex, boron trifluoride trolamine title complex, boron trifluoride piperidines title complex; pyridine-borane complexes, diethanolamine borate, zinc fluoroborate; metal acylate such as stannous octoate or zinc octoate and their any mixture.
Solidifying agent can be with the amount use of cure curable composition epoxy resin effectively, yet, the amount of solidifying agent also will depend on the concrete component that exists in curable epoxy resin composition, for example, epoxy resin diluent (A), resin compound (B) and the solidifying agent that adopts and/or the kind of catalyzer.
Usually, the appropriate amount of solidifying agent can be at about 0.80: 1 to about 1.50: 1, and the equivalents of the epoxy group(ing) in the equivalents/curable epoxy resin composition of the hydrogen atoms in preferred about 0.95: 1 solidifying agent to about 1.05: 1 scope.Hydrogen atoms be can with Resins, epoxy in the hydrogen atom of epoxy reaction.
Similarly, curing catalysts is also with the amount use of cure curable composition epoxy resin effectively, yet, the amount of curing catalysts also will depend on the concrete component that exists in the curable epoxy resin composition, for example, epoxy resin diluent (A), resin compound (B) and the solidifying agent that adopts and/or the kind of catalyzer.
Usually, based on the gross weight of curable epoxy resin composition, in the present invention the appropriate amount of operable curing catalysts can for about 0.0001 weight % to about 2 weight %, and preferred about 0.01 weight % is to about 0.5 weight %.
The curing catalysts that can use one or more in the method for cure curable composition epoxy resin is to accelerate or to change solidification process in addition.
Can also be with curable epoxy resin composition and at least a additive blend, for example, curing catalyst, solvent, the thinner that is different from epoxy resin diluent (A) (comprises, for example, non-reactive diluent, monoepoxide diluents is different from and comprises cis, anti-form-1,3-and-1, epoxy resin diluent and the reactive non-epoxide diluents of those of 4-hexanaphthene dimethyl ether part), properties-correcting agent such as flow ability modifying agent or thickening material, strongthener, filler, pigment, dyestuff, releasing agent, wetting agent, stablizer, fire retardant, tensio-active agent, or their any combination.
These additives can add with the amount of sense equivalent, and for example, pigment and/or dyestuff can add with the amount that the composition required color will be provided.Usually, based on the gross weight of curable epoxy resin composition, the amount of additive can for about 0 weight % to about 20 weight %, preferred about 0.5 weight % is to about 5 weight %, more preferably from about 0.5 weight % is to about 3 weight %.
The curing catalyst that can use in the present invention comprises, and is for example single, two, three and four phenol; Chlorinated phenol; Aliphatic or alicyclic list or dicarboxylic acid; The aromatic carboxylic acid; Hydroxy-benzoic acid; The halogenation Whitfield's ointment; Boric acid; Aromatic sulfonic acid; Imidazoles; Tertiary amine; Amino alcohol; Aminopyridine; Amino-phenol; Mercapto-phenol; With their any mixture.
Specially suitable curing catalyst comprises 2,4-xylenol, 2,6-xylenol, the 4-methylphenol, 4-tert.-butyl phenol, 2-chlorophenol, 4-chlorophenol, 2,4 dichloro phenol, 4-nitrophenols, 1, the 2-dihydroxy-benzene, 1,3-dihydroxy-benzene, 2,2 '-dihydroxybiphenyl, 4,4 '-isopropylidene biphenol, valeric acid, oxalic acid, phenylformic acid, 2,4 dichloro benzene formic acid, the 5-chloro-salicylic acid, Whitfield's ointment, tosic acid, Phenylsulfonic acid, hydroxy-benzoic acid, 4-ethyl-glyoxal ethyline, 1-Methylimidazole, triethylamine, Tributylamine, N, N-diethylethanolamine, N, the N-dimethyl benzylamine, 2,4,6-three (dimethylamino) phenol, 4-dimethylaminopyridine, 4-amino-phenol, the 2-amino-phenol, 4-mercapto-phenol, or their any combination.
The example that can be used for the present invention's solvent comprises, for example, and aliphatic series and aromatic hydrocarbon, halogenated aliphatic hydrocarbon, aliphatic ether, fatty nitrile, cyclic ether, glycol ether, ester, ketone, acid amides, sulfoxide and their any combination.
Specially suitable solvent comprises pentane, hexane, and octane, toluene, dimethylbenzene, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), N, dinethylformamide, methyl-sulphoxide, Anaesthetie Ether, tetrahydrofuran (THF), 1,4-two Alkane, methylene dichloride, chloroform, Ethylene Dichloride, trichloroethane, ethylene glycol dimethyl ether, glycol ether methyl ether, dipropylene glycol methyl ether, N-Methyl pyrrolidone, N,N-dimethylacetamide, acetonitrile, tetramethylene sulfone and their any combination.
The example that can be used for the present invention's the thinner except Resins, epoxy thinner (A) comprises, for example, and dibutyl phthalate, dioctyl phthalate (DOP), vinylbenzene, low-molecular-weight polystyrene, Styrene oxide 98min., glycidyl allyl ether, phenyl glycidyl ether, butylglycidyl ether, vinyl epoxy hexane, neopentylglycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, the glycol ether diglycidylether, dipropylene glycol diglycidylether, poly-(propylene glycol) diglycidylether, the thiodiglycol diglycidylether, maleic anhydride, ε-Ji Neixianan, butyrolactone, vinyl cyanide and their any combination.
The specially suitable thinner that is different from epoxy resin diluent (A) comprises, for example, except comprising cis, anti-form-1,3-and-1, nominal bifunctional epoxy resin thinner beyond those of 4-hexanaphthene dimethyl ether part, above-mentioned neopentylglycol diglycidyl ether for example, butanediol diglycidyl ether, hexanediol diglycidyl ether, the glycol ether diglycidylether, dipropylene glycol diglycidylether, poly-(propylene glycol) diglycidylether, thiodiglycol diglycidylether and their any combination.
Based on the gross weight of curable epoxy resin composition, properties-correcting agent such as thickening material and flow ability modifying agent can be with 0 to about 10, and preferably, about 0.5 to about 6, and more preferably from about 0.5 to about 4 weight % amount is used.
The strongthener that can be used for the present invention comprises natural and synthon, and form is yarn fabric, pad, monofilament, multifilament, unidirectional fiber, rove, random fiber or long filament, mineral filler or palpus, or hollow ball.Other suitable strongthener comprises glass, carbon, pottery, nylon, regenerated fiber, cotton, aromatic poly, graphite, polyalkylene terephthalate, polyethylene, polypropylene, polyester and their any combination.
Can comprise for the present invention's filler, for example, inorganic oxide, ceramic microsphere, plastic microsphere, glass microsphere, inorganic palpus, calcium carbonate and their any combination.
Based on the gross weight of curable epoxy resin composition, filler can be with about 0 weight % to about 95 weight %, and preferred about 10 weight % are to about 80 weight %, and more preferably from about 40 weight % are to the amount use of about 60 weight %.
According to the present invention, the method by the cure curable composition epoxy resin prepares cured epoxy resin.
The method of solidifying curable epoxy resin composition of the present invention can or be lower than under the pressure of atmosphere and about 0 ℃ to about 300 ℃ at atmosphere, super large gas, preferred about 25 ℃ to about 250 ℃, more preferably from about 50 ℃ extremely about 200 ℃ temperature carry out.
The required time of method of finishing the cure curable composition epoxy resin is depended on the temperature of employing.Higher temperature needs short set time, and lower temperature needs long set time.Usually, this method can preferred about 15 minutes to about 24 hours, more preferably from about be finished in 30 minutes to about 12 hours at about 1 minute to about 48 hours.
Also exercisable is that partly solidified curable epoxy resin composition of the present invention solidifies the second stage product in the time after a while subsequently fully to form the second stage product.
Have been found that, with only comprise cis, anti-form-1, the Resins, epoxy reactive diluent of 4-cyclohexanedimethanol is compared, and Resins, epoxy reactive diluent composition of the present invention had low-down viscosity and do not show crystallization after the storage time of room temperature and prolongation under the situation of not using solvent.In addition, more of the present invention comprise subchloride (ion, hydrolyzable and amount to) the Resins, epoxy reactive diluent composition of the Resins, epoxy reactive diluent of form, provide raising and reactivity conventional epoxy curing agent to Resins, epoxy reactive diluent composition, the potential corrosion that reduces and the electrical property that improves.
Found that also based on cis, anti-form-1, the cured epoxy resin of 4-hexanaphthene dimethyl ether part is compared with only, cured epoxy resin of the present invention has the special improvement aspect physics and mechanical properties.For example, cured epoxy resin of the present invention has high glass-transition temperature, the wet fastness of improvement and erosion resistance and the coating character of improving; And it is compatible with conventional epoxy curing agent.
As shown in following examples and the comparison test, only comprise cis, anti-form-1, the cured epoxy resin (do not contain oligopolymer or contain one or more oligopolymer) of 4-hexanaphthene dimethyl ether part may have the double glass transition temperature of not expecting.Yet when with cis, anti-form-1,3-and 1,4-hexanaphthene dimethyl ether part are not observed the double glass transition temperature during for the preparation of cured epoxy resin of the present invention.In addition, and only comprise cis, anti-form-1, the cured epoxy resin of 4-hexanaphthene dimethyl ether part is compared, and cured epoxy resin of the present invention can have at about 21.5% the second-order transition temperature of raising to about 48.7% scope.
As also in the following example and comparison test, showing, only comprise cis, anti-form-1 with respect to using, the corresponding coating of the Resins, epoxy preparation of 4-hexanaphthene dimethyl ether part, use the coating of Resins, epoxy reactive diluent preparation of compositions of the present invention can show better coating quality, the resistivity of improving to solvent such as methyl ethyl ketone, the hardness that improves, higher shock resistance and resistance to bending do not have the adhesivity loss.
The application of cured epoxy resin can be included in electricity or structural laminated body or complex body, and long filament twines body (filament winding), moulding bodies (molding), foundry goods, package, coating, the application in waiting.
Embodiment
Abbreviation
In embodiment and comparison test, use following standardized abbreviations:
GC=gas-chromatography (chromatogram)
GPC=gel permeation chromatography (chromatogram)
DSC=dsc (calorimetric)
The EEW=epoxy equivalent (weight)
The RSD=relative standard deviation
DI=is deionized
The eq=equivalent
Wt=weight
Min=minute
Hr=hour
The mg=milligram
The g=gram
The mL=milliliter
The mm=millimeter
The cp=centipoise
The CHDM=cis-, anti-form-1,3-and 1,4 cyclohexane dimethanol
CHDM MGE=cis, anti-form-1, the monoglycidyl ether of 3-and 1,4 cyclohexane dimethanol
CHDM DGE=cis, anti-form-1, the diglycidylether of 3-and 1,4 cyclohexane dimethanol
The diglycidylether of DGE BPA=dihydroxyphenyl propane
The CHDM that uses in following examples and comparison test is commercial grades, UNOXOL TMDiol (produce and sell by Dow Chemical (The Dow Chemical Company)).The GC of CHDM analyzes the 0.5 area % surplus that has disclosed the existence of 99.5 area % (for 4 kinds of independent isomer, 22.3,32.3,19.6 and 25.3 area %) and comprised single small amount of impurities.
The DGE BPA that uses in following examples and comparison test is commercial grades, D.E.R. TM331 (produce and sell by Dow Chemical (The Dow Chemical Company)).
D.E.R. be the trade mark of Dow Chemical (The Dow Chemical Company) with UNOXOL.
Analytical equipment and method
In embodiment and comparison test, use following standard analysis equipment and method:
Gas-chromatography (GC) is analyzed
Adopt Hewlett Packard 5890 Series II Plus gas chromatographs, and use DB-1 capillary column (61.4M, 0.25mm, Agilent).Post is remained in the chromatographic instrument baking oven that is in 50 ℃ of initial temperatures.Syringe entrance and flame ionization detector are all remained on 300 ℃.Helium carrier gas stream by post remains on 1.1mL/min.Temperature program(me) adopted 2 minute hold-time of 50 ℃, the outlet temperature of the rate of heating to 300 of 10 ℃/min ℃, and 15min hold-time of 300 ℃.When sample is analyzed when having not from post the oligopolymer of wash-out, before analyzing next sample, the chromatographic instrument baking oven is remained on 300 ℃ of oligopolymer until remnants and " burnouted ".Retention time is denoted as oligopolymer greater than all components of the retention time of 4 kinds of isomer C HDM DGE in the following example and comparison test.Term used herein " component that does not contain oligopolymer " or " being substantially free of the component of oligopolymer " expression, based on the gross weight of Resins, epoxy product, oligopolymer is with less than 2 weight %, and preferably less than 1 weight %, more preferably 0 weight % exists.All GC in following examples and comparison test analyze with area % and measure, because of rather than the quantitative measurment of any given component.
Being used for the sample that GC analyzes prepares by following method: collect from the 0.5mL aliquot sample of the Resins, epoxy product of epoxidizing method, and join in the bottle that contains the 1mL acetonitrile.1mL syringe (Norm-Ject then packs the part of product in the acetonitrile into, whole polypropylene, polyethylene, Henke Sass Wolf GmbH) in, and by syringe filter (Acrodisc CR 13, has 0.2 μ m PTFE film, Pall Corporation, Gelman Laboratories) to remove any inorganic salt or chip.
I.C.I. cone-plate viscosity
Go up in 25 ℃ of definite viscosity at I.C.I. cone-and-plate viscometer (model VR-4540).Viscometer disposes 0-5 pool spindle (model VR-4105) and balance to 25 ℃, is calibrated to 0.Sample is placed on the viscometer, and kept 2 minutes, after 15 seconds, detect viscosity then and carry out reading.Use the fresh aliquot sample of tested concrete product to finish one or many repetition viscosity test.Each time measured average.
Gel permeation chromatography (GPC) is analyzed
The PL-gel mixing E coupled columns (PL-gel Mixed E pair of columns) that remains on 40 ℃ is used with differential refractometer detector (Waters 410) series connection.Flow velocity at 1mL/min uses tetrahydrofuran (THF) as eluent.Volume injected is 100 microlitres.Sample is diluted to the concentration of 0.45-0.50% in tetrahydrofuran (THF).Use Polymer Laboratories Polyethylene Glycol Calibrants, PEG 10, and Lot 16 proofreaies and correct.For M n, M w, M w/ M n, M pAnd M zRSD less than 3%, and for M Z+1RSD is less than 6%.Visual inspection color atlas and select different peak window (peak window) to be used for the independent integration at each peak.Precision is determined by analyzing bipartite sample.M pThe RSD of (molecular weight at peak maximum place) and area % for greater than 10% peak window of the total area less than 1%, and for less than 10% peak window of the total area less than 10%.With the area percentage that so obtains and peak molecular weight on average to be provided at result displayed in the following example and the comparison test.
Hydrolyzable, muriate analysis ion and total
Hydrolyzable chlorination thing results from coupled product (for example, the chloro-hydrin(e) intermediate) usually, its in the process of epoxidizing method not via with the dehydrochlorination of sodium hydroxide cyclisation so that the epoxide ring to be provided.
The ion muriate comprises the sodium-chlor by product from epoxidizing method, and it is entrained in the Resins, epoxy product.Sodium-chlor produces in the dehydrochlorination of chloro-hydrin(e) and sodium hydroxide jointly.
The explanation of total muriate is attached to chlorine in the epoxy resin structural with the chloromethyl form.Chloromethyl is as the result of the linked reaction of the secondary hydroxyl in the chloro-hydrin(e) intermediate and epihalohydrin (epi) and form.
Ion and hydrolyzable chlorination thing use titration method to determine, and total muriate is determined via x-ray fluorescence analysis.
Epoxy per-cent/epoxy equivalent (weight) (EEW) is analyzed
Use standard titration method is determined the epoxy per-cent in various Resins, epoxy.With samples weighing (in the scope of about 0.1-0.2g) and be dissolved in the methylene dichloride (15mL).Tetraethyl-ammonium bromide solution (15mL) in acetic acid is added in the sample.The solution that obtains is handled with 3 crystal violet solutions (0.1%w/v is in acetic acid), and at Metrohm 665 Dosimat titration apparatuss (Brinkmann) perchloric acid titration of 0.1N in acetic acid.The titration of blank sample provides the solvent background correction, and described blank sample comprises methylene dichloride (15mL) and the tetraethyl-ammonium bromide solution (15mL) in acetic acid.The general method that is used for this titration finds in scientific and technical literature, for example, Jay, R.R., " direct titration of epoxy compounds and aziridine (Direct Titration of Epoxy Compounds and Aziridines) ", analytical chemistry (Analytical Chemistry), 36,3,667-668 (in March, 1964).
Dsc (DSC)
Adopt DSC 2910 Modulated DSC (TA Instruments), flow down with 45 cubic centimetres/min flowing nitrogen use 7 ℃/min heating rate from 25 ℃ to 250 ℃.Concrete example weight is provided in the following example and the comparison test.
Following examples and comparison test further are shown specifically the present invention, limit the scope of the invention but should not be construed as.
Embodiment 1-does not contain CHDM MGE and CHDM DGE mixture and the DGE of oligopolymer
The 10/90 weight % of BPA and the preparation of 50/50 weight % blend and alicyclic diamine cured product thereof And sign
Do not contain the CHDM MGE of oligopolymer and the GC analysis of CHDM DGE mixture and disclosed 13.85 area %CHDM MGE (for 4 kinds of independent isomer, 4.11,2.51,5.08 and 2.15 area %), 83.29 area %CHDM DGE is (for independent isomer, 25.57,29.95,9.45, with 8.32 area %), surplus comprises 11 kinds of small amount of impurities of 2.86 area %.Titration shows 31.66% epoxide (135.93EEW).Viscosity (25 ℃) average out to 36cp.Commercial grade DGEBPA is 23.01% epoxide (187.04EEW) by titrimetry.The nominal viscosity of DGE BPA is 12,500cp (25 ℃).Use these components, prepare blend and characterize as follows:
Figure BPA00001257566000161
a3190,3100 and the mean value of 3000cp, b273,261,272 and the mean value of 271cp
The aliquot sample of each and the solidifying agent of preparation in the mixture are merged, and described solidifying agent comprises and is less than 36% isophorone diamine, is less than 30% benzylalcohol and is less than other composition of 24%, comprises the 4-tert.-butyl phenol.The solidifying agent that uses is the commercial grade amine product, and its Ahew is 120 (Ancamine TM2423, Air Products and Chemicals, Inc.).The dsc analysis that uses 10.7 and 10.4mg of the 13.4mg part of 10/90 weight % blend and 50/50 weight % blend partly to finish characterizes heat release and solidifies.Allow the remainder of every kind of blend in self-vulcanizing, then after fixing 1 hour in being preheated to 150 ℃ baking oven.Use partly reaches from the 30.7mg of the cured product of 50/50 weight % blend and dsc analysis that 29.4mg partly finishes from the 31.8mg of the cured product of 10/90 weight % blend and 32.5mg second-order transition temperature as showing in following table is provided:
a57.9 ℃ and 54.6 ℃ mean value, b46.4 ℃ and 44.0 ℃ mean value, c80.8 ℃ and 81.5 ℃ mean value,
d327.62 the mean value of joule/g and 322.2 joules/g, e38.7 ℃ and 38.3 ℃ mean value
Cured product from 10/90 and 50/50 weight % blend is rigidity, light yellow, transparent solid.
Comparison test A-cis, anti-form-1, the list that does not contain oligopolymer of 4-cyclohexanedimethanol mixture With the 10/90 and 50/50 weight % of diglycidylether and DGE BPA wet thing and alicyclic altogether The preparation of diamines cured product and sign
Cis, trans 1, the list that does not contain oligopolymer of 4-cyclohexanedimethanol mixture and the GC of diglycidylether analyze and have disclosed 13.90 area % cis, trans 1, the monoglycidyl ether of 4-cyclohexanedimethanol is (for 2 kinds of independent isomer, 8.37 and 5.53 area %), 85.55 area % cis, trans 1, the diglycidylether of 4-cyclohexanedimethanol (for 2 kinds of independent isomer, 28.46 and 57.09 area %), surplus comprises 7 kinds of small amount of impurities of 0.55 area %.Titration shows 31.45% epoxide (136.83EEW).Viscosity (25 ℃) average out to 36cp.Commercial grade DGE BPA is described among the embodiment 1.Use these components, prepare blend and characterize as follows:
Figure BPA00001257566000172
a3030 and the mean value of 3050cp, the mean value of b 270 and 272.5cp
With in the mixture each aliquot sample and embodiment 1 in the solidifying agent described merge.Use 14.3 and the 11.5mg part of 10/90 weight % blend and the 12.3mg of 50/50 weight % blend and the dsc analysis that 14.4mg partly finishes to characterize heat release curing.Allow the remainder of every kind of blend in self-vulcanizing, then after fixing 1 hour in being preheated to 150 ℃ baking oven.Use partly reaches from the 27.4mg of the cured product of 50/50 weight % blend and dsc analysis that 26.4mg partly finishes from the 28.6mg of the cured product of 10/90 weight % blend and 31.6mg second-order transition temperature as shown in following table is provided:
a37.7 ℃ and 38.8 ℃ mean value, b79.2 ℃ and 80.1 ℃ mean value,
c321.7 the mean value of joule/g and 325.0 joules/g,
dObserve dual Tg, 46.25 ℃ add 59.22 ℃ with 45.62 ℃ of mean values that add 58.27 ℃,
e36.9 ℃ and 40.9 ℃ mean value, f82.3 ℃ and 82.3 ℃ mean value,
g325.7 the mean value of joule/g and 314.1 joules/g
hObserve dual Tg, 31.00 ℃ add 41.99 ℃ and 33.55 ℃ of mean values that add 39.98 ℃
Cured product from 10/90 and 50/50 weight % blend is rigidity, and is light yellow, transparent solid.
Embodiment 2-contains CHDM MGE and CHDM DGE mixture and the DGE of oligopolymer component 10/90, the 25/75 and 50/50 weight % blend of BPA and the system of alicyclic diamine cured product thereof Be equipped with and sign
Contain the CHDM MGE of oligopolymer component and the GC analysis of CHDM DGE mixture and disclosed 2.8 area %CHDM MGE (for 4 kinds of independent isomer, 0.6,0.4,1.0, with 0.8 area %), 94.7 area %CHDM DGE is (for 4 kinds of independent isomer, 21.9,34.7,11.2, with 26.9 area %), 1.7 area % oligopolymer (4 kinds of a small amount of components), surplus comprises 3 kinds of small amount of impurities.Titration shows 28.71% epoxide (149.89EEW).Viscosity (25 ℃) average out to 137cp.Commercial grade DGE BPA is described among the embodiment 1.Use said components, prepare blend and characterize as follows:
Figure BPA00001257566000191
a3800,3750 and the mean value of 3700cp, b1920,1950 and the mean value of 1900cp,
c590 and the mean value of 530cp
Aliquot sample and the solidifying agent described in the embodiment 1 of each in the mixture merged.Use 11.4mg and the 11.3mg part of 10/90 weight % blend, 12.2 and the 10.9mg part of 25/75 weight % blend and the 13.3mg of 50/50 weight % blend and the dsc analysis that 12.2mg partly finishes characterize heat release and solidify.Allow the remainder of every kind of blend in self-vulcanizing, then after fixing 1 hour in being preheated to 150 ℃ baking oven.Use is from 31.4mg and the 28.9mg part of the cured product of 10/90 weight % blend, and partly reaching from the 32.7mg of the cured product of 50/50 weight % blend and dsc analysis that 29.1mg partly finishes from the 27.9mg of the cured product of 25/75 weight % blend and 30.9mg provides second-order transition temperature as shown in following table:
Figure BPA00001257566000192
a37.4 with 39.5 ℃ mean value, b79.1 with 79.5 ℃ mean value, c351.4 with the mean value of 331.9 joules/g,
d62.7 ℃ and 62.4 ℃ mean value, e38.8 with 36.3 ℃ mean value, f80.9 with 79.2 ℃ mean value,
g333.3 with the mean value of 351.0 joules/g, h46.8 with 48.3 ℃ mean value, i38.9 with 40.5 ℃ mean value,
j81.2 with 81.0 ℃ mean value, k344.0 with the mean value of 364.2 joules/g, l42.8 and 43.4 ℃ mean value
Comparison test B-contains cis, the anti-form-1 of oligopolymer component, the list of 4-cyclohexanedimethanol mixture Reach with 10/90, the 25/75 and 50/50 weight % blend of diglycidylether and DGE BPA The preparation of its alicyclic diamine cured product and sign
The cis that contains the oligopolymer component, trans 1, the GC of the monoglycidyl ether of 4-cyclohexanedimethanol and the mixture of diglycidylether analyzes and has disclosed 1.6 area % cis, anti-form-1, the 4-cyclohexanedimethanol is (for 2 kinds of independent isomer, 0.3 and 1.3 area %), 7.8 area % cis, anti-form-1, the monoglycidyl ether of 4-cyclohexanedimethanol (for 2 kinds of independent isomer, 4.7 and 3.1 area %), 61.2 area % cis, anti-form-1, the diglycidylether of 4-cyclohexanedimethanol (for 2 kinds of independent isomer, 19.1 and 42.1 area %), 29.2 area % oligopolymer are (for 9 kinds of independent components, 0.63,1.35,1.44,0.68,7.20,17.30,0.22,0.21, with 0.20 area %), wherein 0.2 area % surplus is single impurity.Titration shows 27.05% epoxide (159.05EEW).Viscosity (25 ℃) average out to 69cp.Analyze and ion obtain 536ppm hydrolyzable chlorination thing with hydrolyzable and total muriate, 21.60ppm ion muriate and 2.356% total muriate.Gpc analysis provides following result: M n=245, M w=265, M w/ M n=1.08, M p=205, M z=292, M Z+1=331.The integration of the peak window at each peak (peak windows) provides following result:
The peak window Mp Area %
A 205 56.1
B 308 33.9
C 401 8.5
D The 400-1000MW afterbody 2.0
Commercial grade DGE BPA is described among the embodiment 1.Use said components, prepare blend and characterize as follows:
Figure BPA00001257566000211
a3650 and the mean value of 3600cp,
b1600 and the mean value of 1620cp,
c412.5 and the mean value of 416.25cp
Aliquot sample and the solidifying agent described in the embodiment 1 of each in the mixture merged.Use 10.2mg and the 12.5mg part of 10/90 weight % blend, the 12.0mg of the 10.5mg of 25/75 weight % blend and 10.5mg part and 50/50 weight % blend and the dsc analysis that 12.6mg partly finishes characterize heat release and solidify.Allow the remainder of every kind of blend in self-vulcanizing, then after fixing 1 hour in being preheated to 150 ℃ baking oven.Use is from 29.9 and 32.7mg part of the cured product of 10/90 weight % blend, partly reaches dsc analysis that 32.2 and 32.8mg from the cured product of 50/50 weight % blend partly finish from the 29.4mg of the cured product of 25/75 weight % blend and 32.2mg second-order transition temperature as shown in following table is provided:
Figure BPA00001257566000212
a38.2 with 36.3 ℃ mean value, b80.0 with 79.9 ℃ mean value, c346.4 with the mean value of 334.8 joules/g,
dObserve dual Tg, 51.33 ℃ add 61.26 ℃ and 51.68 ℃ of mean values that add 58.76 ℃,
e37.3 with 40.9 ℃ mean value, f82.3 with 82.3 ℃ mean value, g343.5 with the mean value of 342.5 joules/g,
h46.5 ℃ and 46.8 ℃ mean value, i35.8 with 40.0 ℃ mean value, j80.0 with 80.3 ℃ mean value,
k368.8 with the mean value of 342.6 joules/g, l41.09 ℃ and 41.67 ℃ mean value
Cured product from 10/90,25/75 and 50/50 weight % blend is rigidity, and is light yellow, transparent solid.
Embodiment 3-contains CHDM MGE and CHDM DGE mixture and the DGE of oligopolymer component 10/90,25/75 and 50/50 weight % blend and the polyalkylene polyamine cured product thereof of BPA Preparation and sign
Contain the CHDM MGE of oligopolymer component and the GC analysis of CHDM DGE mixture and disclosed 3.5 area %CHDM MGE (for 4 kinds of independent isomer, 0.9,0.5,1.5, with 0.6 area %), 90.2 area %CHDM DGE is (for 4 kinds of independent isomer, 22.2,33.1,10.4, with 24.5 area %), 5.4 area % oligopolymer (＞22 kinds of a small amount of components), surplus is several small amount of impurities.Titration shows 30.41% epoxide (141.52EEW).Viscosity (25 ℃) average out to 76cp.Analyze and ion obtain 83ppm hydrolyzable chlorination thing with hydrolyzable and total muriate, 8.156ppm ion muriate and 0.2304% total muriate.Gpc analysis provides following result: M n=239, M w=335, M w/ M n=1.41, M p=195, M z=708, M Z+1=2010.The integration of the peak window at each peak provides following result:
The peak window Mp Area %
A 195 71.1
B 326 3.5
C 446 13.8
D 651 4.8
E 830 2.4
F The 1000-6500MW afterbody 4.7
Commercial grade DGE BPA is described among the embodiment 1.Use said components, prepare blend and characterize as follows:
Figure BPA00001257566000231
a3150,3300 and the mean value of 3190cp,
b1700 and the mean value of 1780cp,
c520,510 and the mean value of 570cp
With in the mixture each aliquot sample with merge as the Triethylenetetramine (TETA) of solidifying agent.The solidifying agent that uses is commercial grades, and its Ahew is 24.4 (D.E.H. TM24, Dow Chemical (The Dow Chemical Company)).Use 11.8 and 11.8mg part of 10/90 weight % blend, the 10.7mg of the 11.3mg of 25/75 weight % blend and 12.0mg part and 50/50 weight % blend and the dsc analysis that 11.2mg partly finishes characterize heat release and solidify.Allow the remainder of every kind of blend in self-vulcanizing, then after fixing 1 hour in being preheated to 150 ℃ baking oven.Use is from the 31.4mg of the cured product of 10/90 weight % blend, 31.7mg and the 34.6mg part, partly reaching from the 33.0mg of the cured product of 50/50 weight % blend and dsc analysis that 31.0mg partly finishes from the 28.9mg of the cured product of 25/75 weight % blend and 28.0mg provides second-order transition temperature as shown in following table:
Figure BPA00001257566000232
a64.0 with 62.6 ℃ mean value, b96.6 with 95.9 ℃ mean value, c553.0 with the mean value of 540.6 joules/g,
d113.9,111.5 and 111.1 ℃ mean value, e63.5 with 62.0 ℃ mean value, f97.3 with 96.2 ℃ mean value,
g506.2 with the mean value of 555.1 joules/g, h104.0 with 100.4 ℃ mean value, i65.9 with 68.5 ℃ mean value,
j100.7 with 101.3 ℃ mean value, k587.0 with the mean value of 616.1 joules/g, l84.9 and 82.1 ℃ mean value
Cured product from 10/90,25/75 and 50/50 weight % blend is rigidity, and is light yellow, transparent solid.
Comparison test C-contains cis, the anti-form-1 of oligopolymer component, the list of 4-cyclohexanedimethanol mixture Reach with 10/90, the 25/75 and 50/50 weight % blend of diglycidylether and DGE BPA The preparation of its polyalkylene polyamine cured product and sign
The cis, the anti-form-1 that contain the oligopolymer component, list and the diglycidylether of 4-cyclohexanedimethanol mixture are described among the comparison test B.Commercial grade DGE BPA is described among the embodiment 1.Use said components, prepare blend and characterize as follows:
Figure BPA00001257566000241
aReferring to the viscosity data that provides among the comparison test B
Aliquot sample and the solidifying agent described in the embodiment 3 of each in the mixture merged.Use 12.5mg and the 10.1mg part of 10/90 weight % blend, the 11.2mg of the 10.2mg of 25/75 weight % blend and 12.1mg part and 50/50 weight % blend and the dsc analysis that 12.4mg partly finishes characterize heat release and solidify.Allow the remainder of every kind of blend in self-vulcanizing, then after fixing 1 hour in being preheated to 150 ℃ baking oven.Use is from 30.4 and 33.2mg part of the cured product of 10/90 weight % blend, and partly reaching from the 33.7mg of the cured product of 50/50 weight % blend and dsc analysis that 31.5mg partly finishes from the 28.9mg of the cured product of 25/75 weight % blend and 29.9mg provides second-order transition temperature as shown in following table:
Figure BPA00001257566000251
a63.0 with 60.9 ℃ mean value, b95.5 with 94.9 ℃ mean value, c534.0 with the mean value of 534.9 joules/g,
d109.1 ℃ and 108.9 ℃ mean value, e63.6 with 64.3 ℃ mean value, f97.3 with 97.5 ℃ mean value,
g544.8 with the mean value of 499.3 joules/g, h93.0 with 93.7 ℃ mean value, i58.4 with 61.7 ℃ mean value,
j96.3 with 97.0 ℃ mean value, k540.9 with the mean value of 577.9 joules/g,
lObserve dual Tg, 55.07 ℃ add 73.54 ℃ and 57.20 ℃ of mean values that add 71.25 ℃
Cured product from 10/90,25/75 and 50/50 weight % blend is rigidity, and is light yellow, transparent solid.
Embodiment 4-does not contain CHDM MGE and CHDM DGE mixture and the DGE BPA of oligopolymer 10/90,25/75 and 50/50 weight % blend and the system of polyalkylene polyamine cured product Be equipped with and sign
Not containing the CHDM MGE of oligopolymer and CHDM DGE mixture and DGE BPA is described among the embodiment 1.Use said components, prepare blend and characterize as follows:
Figure BPA00001257566000252
aReferring to the viscosity data that provides among the embodiment 1
Aliquot sample and the solidifying agent described in the embodiment 3 of each in the mixture merged.Use 10.9mg and the 10.4mg part of 10/90 weight % blend, 10.0 and the 9.9mg part of 25/75 weight % blend and the 10.0mg of 50/50 weight % blend and the dsc analysis that 11.8mg partly finishes characterize heat release and solidify.Allow the remainder of every kind of blend in self-vulcanizing, then after fixing 1 hour in being preheated to 150 ℃ baking oven.Use is from 31.6mg and the 28.0mg part of the cured product of 10/90 weight % blend, and partly reaching from the 31.8mg of the cured product of 50/50 weight % blend and dsc analysis that 31.9mg partly finishes from the 33.4mg of the cured product of 25/75 weight % blend and 31.9mg provides second-order transition temperature as shown in following table:
Figure BPA00001257566000261
a60.1 with 59.6 ℃ mean value, b94.1 with 94.1 ℃ mean value, c563.2 with the mean value of 544.3 joules/g,
d108.8 with 108.0 ℃ mean value, e62.1 with 60.5 ℃ mean value, f96.0 with 94.5 ℃ mean value,
g600.7 with the mean value of 597.2 joules/g, h102.3 with 105.5 ℃ mean value, i60.2 with 62.1 ℃ mean value,
j96.1 with 96.6 ℃ mean value, k586.3 with the mean value of 622.7 joules/g, l71.0 and 71.6 ℃ mean value
Cured product from 10/90,25/75 and 50/50 weight % blend is rigidity, and is light yellow, transparent solid.
Comparison test D-cis, anti-form-1, the list that does not contain oligopolymer and two of 4-cyclohexanedimethanol mixture 10/90, the 25/75 and 50/50 weight % blend of glycidyl ether and DGEBPA and poly- The preparation of alkylene polyamine cured product and sign
The cis, the anti-form-1 that contain the oligopolymer component, single Racemic glycidol and the diglycidylether of 4-cyclohexanedimethanol mixture are described among the comparison test A.Commercial grade DGE BPA is described among the embodiment 1.Use said components, prepare blend and characterize as follows:
aReferring to the viscosity data that provides among the comparison test A
Aliquot sample and the solidifying agent described in the embodiment 3 of each in the mixture merged.Use 10.7mg and the 12.8mg part of 10/90 weight % blend, the 11.7mg of the 10.5mg of 25/75 weight % blend and 12.8mg part and 50/50 weight % blend and the dsc analysis that 12.9mg partly finishes characterize heat release and solidify.Allow the remainder of every kind of blend in self-vulcanizing, then after fixing 1 hour in being preheated to 150 ℃ baking oven.Use is from 33.6mg and the 30.4mg part of the cured product of 10/90 weight % blend, partly reaches dsc analysis that 30.7 and 26.5mg from the cured product of 50/50 weight % blend partly finish from the 29.6mg of the cured product of 25/75 weight % blend and 32.9mg second-order transition temperature as shown in following table is provided:
Figure BPA00001257566000272
a60.5 with 60.8 ℃ mean value, b94.4 with 93.7 ℃ mean value, c506.5 with the mean value of 547.8 joules/g,
d108.9 with 109.8 ℃ mean value, e60.9 with 61.0 ℃ mean value, f94.6 with 95.2 ℃ mean value,
g536.9 with the mean value of 578.6 joules/g, h97.1 with 97.6 ℃ mean value, i58.7 with 61.4 ℃ mean value,
j94.8 with 96.1 ℃ mean value, k594.0 with the mean value of 614.3 joules/g,
lObserve dual Tg, 55.85 ℃ add 75.79 ℃ and 56.77 ℃ of mean values that add 79.45 ℃
Cured product from 10/90,25/75 and 50/50 weight % blend is rigidity, and is light yellow, transparent solid.
Embodiment 5-contains the CHDM MGE of oligopolymer component and CHDM DGE and DGE BPA's Preparation and the sign of 25/75 weight % blend and carboxylic acid anhydride cured product thereof
The CHDM MGE and the CHDM DGE mixture that contain the oligopolymer component are described among the embodiment 3.Commercial grade DGE BPA is described among the embodiment 1.Use said components, prepare blend and characterize as follows:
Figure BPA00001257566000281
The aliquot sample of mixture is merged with solidifying agent and catalyzer.The solidifying agent that uses is commercial grade six hydrogen-4-methylphthalic acid anhydride product, and its molecular weight is 168.19.Equally, the curing catalysts that uses is 117.19 as commercial grade DEAE diethylaminoethanol product, its molecular weight.The 11.0mg of use blend and the dsc analysis that 12.2mg partly finishes characterize heat release and solidify.Allow the remainder of every kind of blend in self-vulcanizing, then after fixing 1 hour in being preheated to 150 ℃ baking oven.Use the 30.4mg of cured product, the dsc analysis that 30.7mg and 30.4mg partly finish provides the second-order transition temperature as shown in following table:
a128.7 with 128.3 ℃ mean value, b149.4 with 148.9 ℃ mean value, c294.1 with the mean value of 343.3 joules/g,
d112.8,119.9 and 116.7 ℃ mean value
Cured product is rigidity, yellow, transparent solid.
Comparison test E-contains cis, the anti-form-1 of oligopolymer component, and 4-cyclohexanedimethanol list and two shrinks The 25/75 weight % blend of glyceryl ether and DGE BPA and the preparation of carboxylic acid anhydride cured product thereof and Characterize
The cis, the anti-form-1 that contain the oligopolymer component, single Racemic glycidol and the diglycidylether of 4-cyclohexanedimethanol mixture are described among the comparison test A.Commercial grade DGE BPA is described among the embodiment 1.Use said components, prepare blend and characterize as follows:
Figure BPA00001257566000291
The aliquot sample of mixture is merged with the solidifying agent described in the embodiment 5 and catalyzer.The 9.5mg of use blend and the dsc analysis that 9.5mg partly finishes characterize heat release and solidify.Allow the remainder of every kind of blend in self-vulcanizing, then after fixing 1 hour in being preheated to 150 ℃ baking oven.The 28.7mg of use cured product and the dsc analysis that 26.6mg partly finishes provide the second-order transition temperature as shown in following table:
a132.5 with 132.6 ℃ mean value, b154.37 with 154.17 ℃ mean value,
c293.1 with the mean value of 273.8 joules/g, d108.0 and 104.8 ℃ mean value
Cured product is rigidity, yellow, transparent solid.
Embodiment 6-uses CHDM MGE and CHDM DGE and the DGE that contains the oligopolymer component The preparation of the 25/75 weight % blend of BPA and the solvent based coating of Triethylenetetramine (TETA) solidifying agent And sign
Apply preparation
60 weight % solids apply preparation and prepare by following method: the CHDM MGE that contains the oligopolymer component described in the embodiment 2 of mixing 3.4126g (25 weight %) and the DGE BPA described in CHDM DGE and the 10.2377g embodiment 1.The solvent solution of the ethylene glycol monobutyl ether of the blend of 13.6503g and 10.3930g and pimelinketone (80/20 volume %) and 2 polyester modification dimethyl silicone polymer surface properties-correcting agent (BYK 310 " surface-modifying agent (Surface Modifier) ", BYK Chemie USA) is merged.Before being about to prepare coating, adding the Triethylenetetramine (TETA) solidifying agent (1.9392g) described in the embodiment 3 in the above-mentioned solution and thoroughly be blended in wherein.
75 weight % solids apply preparation and prepare by following method: mixing 4.9534g (25 weight %) from DGE BPA described in the embodiment 1 of the CHDM MGE that contains the oligopolymer component of embodiment 2 and CHDM DGE and 14.8601g.The solvent solution of the dimethyl silicone polymer surface properties-correcting agent of the ethylene glycol monobutyl ether of the blend of 19.8135g and 7.5428g and pimelinketone (80/20 volume %) and 2 polyester modification is merged.Before being about to prepare coating, adding the Triethylenetetramine (TETA) solidifying agent (2.8148g) described in the embodiment 3 in the above-mentioned solution and thoroughly be blended in wherein.
Coating preparation
Use 60 weight % solid preparations and #28 scraper plate to apply three 11 inches * 5 inches * 0.0089 standard (gauge) tin free steel sheet.Equally, use 75 weight % solid preparations and #28 scraper plate to apply three 11 inches * 5 inches * 0.0089 standard tin free steel sheet.Before coating applies preparation, every block of plate with washing with acetone twice, is placed on 5min in the baking oven that remains in 100 ℃ then, then be cooled to room temperature before use., behind the wet maintenance in chamber 16hr, they are put into the forced air convection type baking oven (forced air convection type oven) that remains on 50 ℃, and keep 2hr therein to provide transparent, inviscid coating at the plate that will apply.Finish further after fixing by following method: plate is kept 2hr at 100 ℃, then plate is kept 1hr at 150 ℃.
Use 75 weight % solid preparations and #48 scraper plate to apply three 12 inches * 4 inches * 0.032 inch cold-rolled steel sheet.Before coating applies preparation, every block of plate with washing with acetone twice, is placed on 5min in the baking oven that remains in 100 ℃ then, then be cooled to room temperature before use., after room temperature keeps 16hr, they are put into the forced air convection type baking oven that remains on 50 ℃, and keep 2hr therein to provide transparent, inviscid coating at the plate that will apply.Finish further after fixing by following method: plate is kept 2hr at 100 ℃, then plate is kept 1hr at 150 ℃.The coated board that obtains like this has the observed slight whiting of the polyalkylene polyamine of use solidifying agent typical case.
Coating characterizes
Use Fisherscope Multi 650C T3.3/GA1.3 film thickness tester to detect the thickness of every block of plate.Before use, the used thickness standard specimen carries out about the inspection of proofreading and correct to instrument and finds up to specification.Face across every block of plate carries out a series of 10 readings.Use the mean thickness of three blocks of each plates of 60 weight % solid preparations preparation to be: 1.018 mils+/-0.030 mil, 1.042 mils+/-0.031 mil and 1.098 mils+/-0.050 mil.Use the mean thickness of three blocks of each plates of 75 weight % solid preparations preparation to be: 1.344 mils+/-0.131 mil, 1.380 mils+/-0.035 mil and 1.274 mils+/-0.030 mil.Every block of plate is pruned 1/2 inch on whole four limits, is cut into 2 inches * 4 inches coupons then, and residuum is cut into
Figure BPA00001257566000311
Inch * 4 inches coupons.Use methyl ethyl ketone double rub test (Methylethylketone Double Rubs Test), ASTM D 4752-87 (5402) is to 2 inches * 4 inches coupon test 100 double rub (double rubs) from every block of plate.By lip pencil instrument test (Pencil Test), ASTM D 3363-74 carries out the film hardness test to 2 inches * 4 inches coupons from every test panel.Adopt the guider (guide) that is used for the lip pencil instrument is remained on proper angle.
Use the mean thickness of three blocks of each plates that 75 weight % solid preparations prepare at cold-rolled steel sheet to be: 2.162 mils+/-0.061 mil, 2.135 mils+/-0.089 mil and 2.025 mils+/-0.081 mil.Every block of plate is cut in half, two coupons are provided.Use distortion (impact) effect test (Effect of Rapid Deformation (Impact) Test) ASTM D 2794-90 test fast from a coupon of every block of plate, the Gardner shock-testing machine that this test use has 4lb.wt and applies the 160in-lbs ability.Test in carrying out preceding (applying impact in coated side) and opposite (applying impact in uncoated side) direction.Use to change 1/8 " tapering spindle pliability test (Conical Mandrel Bend Test) ASTM D 522-93a, method A (modifications) tests second coupon from every block of plate.Use adherent zone test (Adhesion Tape Test) ASTM D 3359-90-test method B-crosscut girdle tests (Cross-cut Tape Test) test from the untapped bight of every coupon of bent spindle test.Use 11 blade cuttves that thereby the plate cutting is produced 3 section lines parts.Use the light microscopy test board.Obtain following result:
The coating testing method The best coating test result that obtains
The 100MEK double rub To no effect 1/ to no effect 2
Lip pencil instrument hardness 5H1，2
Preceding/opposite impact 160/20in-lbs2
1/8 " tapering spindle bending 5mm2，3
Crosscut adheres to 5B2，4
1Use 60 weight % solid preparations, 2Use 75 weight % solid preparations,
3Measurement is from the distance in the crack of the coating of the small end of axle,
45B represents " non-cracking "
Comparison test F-uses cis, the anti-form-1 that contains the oligopolymer component, 4-cyclohexanedimethanol list and two The 25/75 weight % blend of glycidyl ether and DGE BPA and Triethylenetetramine (TETA) solidifying agent The preparation of solvent based coating and sign
Apply preparation
Prepare 60 weight % solids by following method and apply preparation: mix 3.3895g (25 weight %) at the cis that contains the oligopolymer component, the anti-form-1 described in the comparison test B, DGE BPA described in the embodiment 1 of 4-cyclohexanedimethanol list and diglycidylether and 10.1686g.The titration of the aliquot sample of blend shows 24.41% epoxide (176.26EEW).With the 13.1291g part of blend and the solvent solution merging of the ethylene glycol monobutyl ether of 9.9644g and the dimethyl silicone polymer surface properties-correcting agent of pimelinketone (80/20 volume %) and 2 polyester modifications (BYK 310 " surface-modifying agent (Surface Modifier) ", BYK Chemie USA).Before being about to prepare coating, adding the Triethylenetetramine (TETA) solidifying agent (1.8175g) described in the embodiment 3 in the above-mentioned solution and thoroughly be blended in wherein.
Prepare 75 weight % solids by following method and apply preparation: mix the cis that contains the oligopolymer component, the anti-form-1 described in 4.9559g (25 weight %) the comparison test B, the DGE BPA described in the embodiment 1 of 4-cyclohexanedimethanol list and diglycidylether and 14.8677g.The solvent solution of the dimethyl silicone polymer surface properties-correcting agent of the ethylene glycol monobutyl ether of the blend of 19.8236g and 7.5226g and pimelinketone (80/20 volume %) and 2 polyester modifications is merged.Before being about to prepare coating, adding the Triethylenetetramine (TETA) solidifying agent (2.7442g) described in the embodiment 3 in the above-mentioned solution and thoroughly be blended in wherein.
Coating preparation
Use 60 and 75 weight % solid preparations to apply tin free steel sheet as described in example 6 above.The coated board that obtains like this has the observed slight whiting of the polyalkylene polyamine of use solidifying agent typical case.In addition, opposite with the Clear coating that in plate, obtains, thus about 0.5 inch border variable color of every block of plate provides amber.
Coating characterizes
Test coated board as described in example 6 above.Use the mean thickness of three blocks of each plates of 60 weight % solid preparations preparation to be: 1.018 mils+/-0.030 mil, 1.042 mils+/-0.031 mil and 1.098 mils+/-0.050 mil.Use the mean thickness of three blocks of each plates of 75 weight % solid preparations preparation to be: 1.344 mils+/-0.131 mil, 1.380 mils+/-0.035 mil and 1.274 mils+/-0.030 mil.Use the mean thickness of three blocks of each plates that 75 weight % solid preparations prepare at cold-rolled steel sheet to be: 2.162 mils+/-0.061 mil, 2.135 mils+/-0.089 mil and 2.025 mils+/-0.081 mil.Obtain following result:
The coating testing method The best coating test result that obtains
The 100MEK double rub 1/ slight damage 2 to no effect
Lip pencil instrument hardness 3H1，2
Preceding/opposite impact 160/10in-lbs2
1/8 " tapering spindle bending 8mm2，3
Crosscut adheres to 5B2，4
1Use 60 weight % solid preparations, 2Use 75 weight % solid preparations,
3Measurement is from the distance in the crack of the coating of the small end of axle,
45B represents " non-cracking "
Embodiment 7
A. use the CHDM MGE contain the oligopolymer component and CHDM DGE and DGE BPA The preparation of transparent, no filler (unfilled) foundry goods of 25/75 weight % blend and polyamide curing agent And sign
Masterbatch prepares by following method: mix 50.00g (25 weight %) from the CHDM MGE that contains the oligopolymer component of embodiment 2 and the DGEBPA of CHDM DGE and 150.00g.The diglycidylether of the dihydroxyphenyl propane that uses is commercial grades, and it contains 23.383% epoxide (184.02EEW) by titration.The titration of the aliquot sample of blend shows 25.17% epoxide (170.97EEW).
Before being about to prepare foundry goods, a part (22.00g, 0.1287 epoxy equivalent (weight)) and polyamide curing agent (14.67g, 0.1287 amine hydrogen eq) merging with above-mentioned blend for masterbatches thoroughly mix it therein.The solidifying agent that uses is commercial grades, and its nominal amine hydrogen eq wt is 114 (Ancamide TM2353, Air Products and Chemicals, Inc.).Uniform mixture is placed under the bell jar, and before the preparation foundry goods, applies vacuum to remove all bubbles.The mixture of the degassing is poured in the mould, remain on room temperature then and last ensuing 16hr, so that ambient temperature curing to be provided.The mould that uses is made of 6 inches * 6 inches aluminium sheets.The surface of every block of plate is covered by 6 inches * 6 inches the aluminium flake that is coated with epoxy silicon azane (siloxazane) polymkeric substance.The inner packing ring of 1/8 inch spacing frame of " U "-shape and " U "-shape is between two aluminum dipping form release sheets.Packing ring is formed by the copper cash that wraps in the silicone rubber sleeve.With a series of compression clamps mould is fixed together.Use follow procedure in mould with ambient temperature curing foundry goods after fixing: (a) mould is put into remained on 50 ℃ baking oven and keep 30min therein, (b) improve oven temperature and be set to 100 ℃ (needing 16-20min to reach 100 ℃), (c) keep 60min at 100 ℃, (d) from 100 ℃ of baking ovens, shift out and mould put into the baking oven that remains on 150 ℃, (e) keep 60min at 150 ℃, (f) shift out mould and allow it to be cooled to room temperature, (g) in case be cooled to room temperature just with the foundry goods demoulding.
Use wet saw (wet saw) (Micro-matic Precision Slicing and Dicing Machine, model number WMSA.1015, configuration Digital Measuring Display Dynamics ResearchCorporation, model 700 12DO) with after fixing, transparent, light yellow foundry goods cutting provides five 2.5 inches * 0.5 inch deflection test blocks.Before test, test block is remained on the steady temperature that is in 73.4+/-3.6 ℉ and 50+/-5% relative humidity and the indoor 40hr of humidity.Test uses Instron 4505 to finish according to ASTM D 790, and flexural strength and modulus in flexure are provided.Use the 32.1mg that solidifies foundry goods, the dsc analysis that 28.6mg and 27.2mg partly finish is provided at the second-order transition temperature that shows in the table of embodiment 7 ends.
B. use CHDM MGE and CHDM DGE and the DGE BPA that contains the oligopolymer component 25/75 weight % blend and modification cycloaliphatic amines solidifying agent transparent, the system of no filler foundry goods Be equipped with and sign
Will with the cycloaliphatic amines solidifying agent (14.54g, 0.1287 amine hydrogen eq) of modification merge in the part (22.00g, 0.1287 epoxy equivalent (weight)) of the blend for masterbatches described in above embodiment 7 part A for the preparation of foundry goods.The solidifying agent that uses is commercial grades, and its nominal amine hydrogen eq wt is 113 (Ancamine TM1618, Air Products and Chemicals, Inc.).Use the method for above-mentioned part A, preparation, curing, after fixing foundry goods, and preparation test block and its flexural properties of test.Use the 32.1mg that solidifies foundry goods and the dsc analysis that 32.8mg partly finishes to be provided at the second-order transition temperature that shows in the table of embodiment 7 ends.
C. use CHDM MGE and CHDM DGE and the DGE BPA that contains the oligopolymer component 25/75 w/w % blend and phenylamino alcohol (phenalkamine) solidifying agent transparent, do not have The preparation of filler foundry goods and sign
Will with phenylamino polyol curing agent (14.62g, 0.1170 amine hydrogen eq) merge from the part (20.00g, 0.1170 epoxy equivalent (weight)) of the blend for masterbatches of above-described embodiment 7 part A for the preparation of foundry goods.The solidifying agent that uses is commercial grades, and its nominal amine hydrogen eq wt is 125 (Cardolite
Figure BPA00001257566000351
NC 541LV, Cardolite Corporation).Use the method for above-mentioned part A, preparation, curing, after fixing foundry goods, and preparation test block and its flexural properties of test.Use the 32.2mg that solidifies foundry goods and the dsc analysis that 27.4mg partly finishes to be provided at the second-order transition temperature that shows in the table of embodiment 7 ends.
D. use CHDM MGE and CHDM DGE and the DGE BPA that contains the oligopolymer component 25/75 weight % blend and polyalkylene polyamine solidifying agent transparent, the system of no filler foundry goods Be equipped with and sign
Will with Triethylenetetramine (TETA) solidifying agent (5.00g, 0.2047 amine hydrogen eq) merge from the part (35.00g, 0.2047 epoxy equivalent (weight)) of the blend for masterbatches of above-described embodiment 7 part A for the preparation of foundry goods.The solidifying agent that uses is commercial grades, and its nominal amine hydrogen eq wt is 24.4 (D.E.H. TM24).Use the method for above-mentioned part A, preparation, curing, after fixing foundry goods, and preparation test block and its flexural properties of test.Use the 33.7mg that solidifies foundry goods and the dsc analysis that 34.0mg partly finishes to be provided at the second-order transition temperature that shows in the following table.
Figure BPA00001257566000361
a49.60 48.17 and 48.63 ℃ mean value is not observed the residual solidified energy
b48.73 with 49.08 ℃ mean value, do not observe the residual solidified energy
c53.59 with 52.88 ℃ mean value, do not observe the residual solidified energy
d102.87 with 103.10 ℃ mean value, do not observe the residual solidified energy
Comparison test G
A. use cis, the anti-form-1 that contains the oligopolymer component, 4-cyclohexanedimethanol list and two shrinks sweet The 25/75 weight % blend of oil ether and DGE BPA and polyamide curing agent transparent, no filler The preparation of foundry goods and sign
Prepare masterbatch by following method: mix 50.00g (25 weight %) from the DGEBPA of the cis that contains the oligopolymer component of comparison test B, trans 1,4 cyclohexane dimethanol list and diglycidylether and 150.00g.DGEBPA is described in embodiment 7 part A.The titration of the aliquot sample of blend shows 24.323% epoxide (176.91EEW).
Will with the part (25.00g, 0.1413 epoxy equivalent (weight)) of the above-mentioned blend for masterbatches that merges at polyamide curing agent described in embodiment 7 part A (14.62g, 0.1170 amine hydrogen eq) for the preparation of foundry goods.Use the method for embodiment 7 part A, preparation, curing, after fixing foundry goods, and preparation test block and its flexural properties of test.This preparation can not be cast under the situation of not disperseing bubble.This is can not outgas fully before toppling over foundry goods owing to the high relatively initial viscosity of preparation is feasible.Use to solidify the second-order transition temperature shown in the table that the 31.3mg of foundry goods and dsc analysis that 32.5mg partly finishes be provided at comparison test G end.
In the further trial of the no bubble foundry goods of preparation, a part and the solidifying agent of blend for masterbatches was heated to 50 ℃ respectively before being merged together.As if this provides significantly reduced viscosity, yet preparation produces bubble in Vacuum Degassing Process.Preparation is in lasting degasification process medium viscosity increase and finally become sticking for casting, and still continues to produce bubble.
B. use cis, the anti-form-1 that contains the oligopolymer component, 4-cyclohexanedimethanol list and two shrinks sweet The 25/75 weight % blend of oil ether and DGE BPA and modification cycloaliphatic amines solidifying agent transparent, The preparation of no filler foundry goods and sign
To merge from the cycloaliphatic amines solidifying agent (15.97g, 0.1413 amine hydrogen eq) of the part (25.00g, 0.1413 epoxy equivalent (weight)) of the blend for masterbatches of above part A and the modification of in embodiment 7 part B, describing.Use the method for embodiment 7 part A, preparation, curing, after fixing foundry goods, and preparation test block and its flexural properties of test.Use the 32.8mg that solidifies foundry goods and the dsc analysis that 31.5mg partly finishes to be provided at the second-order transition temperature that shows in the table of comparison test G end.
C. use cis, the anti-form-1 that contains the oligopolymer component, 4-cyclohexanedimethanol list and two shrinks sweet The 25/75 w/w % blend of oil ether and DGE BPA and phenylamino polyol curing agent transparent, The preparation of no filler foundry goods and sign
To merge with phenylamino polyol curing agent (17.66g, 0.1413 amine hydrogen eq) described in embodiment 7 portion C from the part (25.00g, 0.1413 epoxy equivalent (weight)) of the blend for masterbatches of above-mentioned comparison test G part A.Use the method for embodiment 7 part A, preparation, curing, after fixing foundry goods, and preparation test block and its flexural properties of test.Use the 33.8mg that solidifies foundry goods and the DSC that 28.9mg partly finishes to be provided at the second-order transition temperature that shows in the table of comparison test G end.
D. use cis, the anti-form-1 that contains the oligopolymer component, 4-cyclohexanedimethanol list and two shrinks sweet The 25/75 w/w % blend of oil ether and DGE BPA and polyalkylene polyamine solidifying agent thoroughly Bright, the preparation of no filler foundry goods and sign
To merge with the Triethylenetetramine (TETA) solidifying agent (4.83g, 0.19795 amine hydrogen eq) described in the embodiment 7 part D from the part (35.00g, 0.1978 epoxy equivalent (weight)) of the blend for masterbatches of above-mentioned comparison test G part A.Use the method for embodiment 7 part A, preparation, curing, after fixing foundry goods, and preparation test block and its flexural properties of test.Use the 32.7mg that solidifies foundry goods and the DSC that 31.5mg partly finishes to be provided at the second-order transition temperature that shows in the table of comparison test G end.
E. use the transparent of DGE BPA and polyalkylene polyamine solidifying agent, the preparation of no filler foundry goods And sign
Will the part (35.00g, 0.1902 epoxy equivalent (weight)) of the DGE BPA described in embodiment 7 part A with merge at the Triethylenetetramine (TETA) solidifying agent described in the embodiment 7 part D (4.64g, 0.1902 amine hydrogen eq).Use the method for embodiment 7 part A, preparation, curing, after fixing foundry goods, and preparation test block and its flexural properties of test.Use the 32.3mg that solidifies foundry goods and the DSC that 33.7mg partly finishes to be provided at the second-order transition temperature shown in the following table.
Figure BPA00001257566000381
a47.19 with 48.24 ℃ mean value, do not observe the residual solidified energy
b47.82 with 46.87 ℃ mean value, do not observe the residual solidified energy
c51.27 with 50.26 ℃ mean value, do not observe the residual solidified energy
d98.35 with 95.87 ℃ mean value, do not observe the residual solidified energy
e124.92 with 124 ℃ mean value, do not observe the residual solidified energy
Embodiment 8
A. use CHDM MGE and CHDM DGE and the DGE BPA that contains the oligopolymer component 25/75 weight % blend and stroke cure time (Stroke Cure Time) of polyamide curing agent really Fixed
To merge with the polyamide curing agent (0.6749g, 0.00592 amine hydrogen eq) described in embodiment 7 part A from the part (1.0121g, 0.00592 epoxy equivalent (weight)) of the masterbatch of embodiment 7 part A.After thoroughly mixing, immediately the 0.15-0.20g aliquot sample of preparation is coated on the stroke cure hot plate that is preheated to 100 ℃ (Tetrahedron, San Diego, CA) on.Use manual time-keeping each test that (through change) carried out according to ASTM D 4640-86, provide fluid preparation is become thermosetting, rigidity, the time that immovable solid is required.Carry out minimum 3 tests separately, mean value and the sample standard deviation calculated for each test series provide the average stroke cure time.
B. use CHDM MGE and CHDM DGE and the DGE BPA that contains the oligopolymer component 25/75 weight % blend and the determining of stroke cure time of modification cycloaliphatic amines solidifying agent
To merge with the modification cycloaliphatic amines solidifying agent (0.5906g, 0.00523 amine hydrogen eq) described in the embodiment 7 part B from the part (0.8936g, 0.00523 epoxy equivalent (weight)) of the masterbatch of embodiment 7 part A.Use the method for above-described embodiment 8 part A to determine the stroke cure time.
C. use CHDM MGE and CHDM DGE and the DGE BPA that contains the oligopolymer component 25/75 weight % blend and the determining of stroke cure time of phenylamino polyol curing agent
Will from the part (1.3347g, 0.00781 epoxy equivalent (weight)) of the masterbatch of embodiment 7 part A with merge at phenylamino polyol curing agent described in embodiment 7 portion C (0.9758g, 0.00781 amine hydrogen eq).Use the method for above-described embodiment 8 part A to determine the stroke cure time.
D. use CHDM MGE and CHDM DGE and the DGE BPA that contains the oligopolymer component 25/75 weight % blend and stroke cure time of polyalkylene polyamine solidifying agent determine and DSC
To merge with Triethylenetetramine (TETA) solidifying agent (0.1989g, 0.00815 amine hydrogen eq) described in the embodiment 7 part D from the part (1.3939g, 0.00815 epoxy equivalent (weight)) of the masterbatch of embodiment 7 part A.Use the method for above-described embodiment 8 part A to determine the stroke cure time.The 11.1mg of use preparation and the dsc analysis that 10.3mg partly finishes provide the heat release that is attributable to curing to be changed, its maximum value is at 94.63 ℃ and 93.63 ℃ (average 94.13 ℃), be attended by the enthalpy that is respectively 508.0 joules/g and 555.9 joules/g (average 532.0 joules/g).The beginning temperature that this heat release changes is respectively 59.24 ℃ and 57.61 ℃ (average 58.43 ℃).
Indicate The average stroke cure time (min)
Embodiment 8 part A 3.468+/-0.0045
Embodiment 8 part B 6.433+/-0.165
Embodiment 8 portion C 6.024+/-0.0508
Embodiment 8 part D 3.162+/-0.0344
Embodiment 9
A. use CHDM MGE and CHDM DGE and the DGE BPA that contains the oligopolymer component 25/75 weight % blend and polyamide curing agent preparation transparent, no filler foundry goods anti-molten Agent, moisture resistance and erosion resistance test
It is transparent that the method that provides from the described embodiment of use embodiment 7 part A prepares, Do not have FillerFoundry goods cuts one group six 1 inch * 0.5 inch test specimens.All test blocks are wiped clean, weighed then, put into 4 ounces of vials or plastics (high density polyethylene(HDPE)) bottle afterwards, specify as following.Each vial that will hold sample is respectively charged into the methylene dichloride of 50mL, toluene, acetone, or 5 weight % acetic acid in DI water, sealing then.Each Plastic Bottle that will hold sample is respectively charged into the DI water of 50mL or 5 weight % sodium hydroxide (97%) in DI water, then sealing.All bottles are remained on 23.5 ℃, but the bottle that will hold DI water remains in the baking oven that is in 50 ℃.At 24hr, 48hr, 144hr after the 504hr and only for 5% acetic acid, after other 52 days of 5%NaOH and the 50 ℃ of DI water, shifts out each sample, blots, and observes any variation, weighs, and puts back to again then in the bottle, continues test.Obtain following result:
Figure BPA00001257566000401
aCracked behind 7.2hr, stop test, bSolvent in sample " window glass (windowpane) ",
cSolvent " window glass " disappears behind 216hr, rubber-like,
dThere is not solvent " window glass " now, rubber-like, eRubber-like, internal fissure
B. use CHDM MGE and CHDM DGE and the DGE BPA that contains the oligopolymer component 25/75 w/w % blend and modification cycloaliphatic amines solidifying agent preparation transparent, no filler The solvent resistance of foundry goods, moisture resistance and erosion resistance test
It is transparent that the method that provides from the described embodiment of use among embodiment 7 part B prepares, and no filler foundry goods cuts one group six 1 inch * 0.5 inch test specimens.The method that use provides in above-described embodiment 9 part A is tested all test blocks.Obtain following result:
Figure BPA00001257566000411
aCracked behind 7.2hr, stop test, bSolvent in sample " window glass ",
cBreaking in solvent " window glass " stops test, dLittle " bubble " in sample
C. use CHDM MGE and CHDM DGE and the DGE BPA that contains the oligopolymer component 25/75 weight % blend and phenylamino polyol curing agent preparation transparent, no filler foundry goods anti- Solvent borne, moisture resistance and erosion resistance test
It is transparent that the method that provides from the described embodiment of use embodiment 7 portion C prepares, and no filler foundry goods cuts one group six 1 inch * 0.5 inch test specimens.The method that use provides in above-described embodiment 9 part A is tested all test blocks.Obtain following result:
Figure BPA00001257566000412
aCracked behind 7.2hr, stop test, bSolvent in sample " window glass "
cCrack into two, have solvent " window glass ", stop test
dThere is solvent " window glass " in short crack on an angle, stops test
D. use CHDM MGE and CHDM DGE and the DGE BPA that contains the oligopolymer component 25/75 weight % blend and polyalkylene polyamine solidifying agent preparation transparent, no filler foundry goods Solvent resistance, the test of moisture resistance and erosion resistance
It is transparent that the method that provides from the described embodiment of use among embodiment 7 part D prepares, and no filler foundry goods cuts one group six 1 inch * 0.5 inch test specimens.The method that use provides in above-described embodiment 9 part A is tested all test blocks.Obtain following result:
Figure BPA00001257566000421
aEdges broken, cracked, stop test, bEdge chips, cSolvent in sample " window glass "
Comparison test H
A. use cis, the anti-form-1 that contains the oligopolymer component, 4-cyclohexanedimethanol list and two shrinks sweet It is saturating that the 25/75 w/w % blend of oil ether and DGE BPA and polyamide curing agent prepare Bright, the solvent resistance of no filler foundry goods, moisture resistance and erosion resistance test
It is transparent that the method that provides from the described comparison test of use comparison test G part A prepares, and no filler foundry goods cuts one group six 1 inch * 0.5 inch test specimens.The method that use provides in embodiment 9 part A is tested all test blocks.Obtain following result:
Figure BPA00001257566000422
aCracked behind 7.2hr, stop test, bSegment breaks away from an edge,
cSolvent in sample " window glass ", dBreaking in whole 4 angles, stops test,
eThere is not solvent " window glass " now, rubber-like, fEdge chips,
gRubber-like, internal fissure, h" bubble " in sample
B. use cis, the anti-form-1 that contains the oligopolymer component, 4-cyclohexanedimethanol list and two shrinks sweet 25/75 w/w % blend and the modification cycloaliphatic amines solidifying agent system of oil ether and DGE BPA What be equipped with is transparent, the solvent resistance of no filler foundry goods, moisture resistance and erosion resistance test
It is transparent that the method that provides from the described comparison test of use among comparison test G part B prepares, and no filler foundry goods cuts one group six 1 inch * 0.5 inch test specimens.The method that use provides in embodiment 9 part A is tested all test blocks.Obtain following result:
Figure BPA00001257566000431
aCracked behind 7.2hr, stop test, bSolvent in sample " window glass ",
cIn solvent " window glass ", break, cracked, stop test,
d" bubble ", the microfracture in sample
C. use cis, the anti-form-1 that contains the oligopolymer component, 4-cyclohexanedimethanol list and two shrinks sweet The 25/75 w/w % blend of oil ether and DGE BPA and the preparation of phenylamino polyol curing agent Transparent, the solvent resistance of no filler foundry goods, moisture resistance and erosion resistance test
It is transparent that the method that provides from the described comparison test of use comparison test G portion C prepares, and no filler foundry goods cuts one group six 1 inch * 0.5 inch test specimens.The method that use provides in embodiment 9 part A is tested all test blocks.Obtain following result:
Figure BPA00001257566000441
aCracked behind 7.2hr, stop test, bSolvent in sample " window glass ",
cSolvent " window glass ", around solvent " window glass " internal fracture,
dBreak in half, have solvent " window glass ", stop test,
eSolvent " window glass, break, and stops test by whole 4 angles
D. use cis, the anti-form-1 that contains the oligopolymer component, 4-cyclohexanedimethanol list and two shrinks sweet 25/75 w/w % blend and the polyalkylene polyamine solidifying agent system of oil ether and DGEBPA What be equipped with is transparent, the solvent resistance of no filler foundry goods, moisture resistance and erosion resistance test
It is transparent that the method that provides from the described comparison test of use among comparison test G part D prepares, and no filler foundry goods cuts one group six 1 inch * 0.5 inch test specimens.The method that use provides in embodiment 9 part A is tested all test blocks.Obtain following result:
Figure BPA00001257566000442
aEdge chips, bEdge chips, solvent " window glass ", cracked, stop test,
cEdge chips, solvent " window glass "
E. use the transparent of DGE BPA and polyalkylene polyamine solidifying agent preparation, no filler foundry goods Solvent resistance, moisture resistance and erosion resistance test
It is transparent that the method that provides from the described comparison test of use among comparison test G part E prepares, and no filler foundry goods cuts one group six 1 inch * 0.5 inch test specimens.The method that use provides in embodiment 9 part A is tested all test blocks.Obtain following result:
aSolvent in sample " window glass ", its first observed after exposing 72hr arrives,
bSolvent " window glass ", broken after 312hr hour, stop test,
Embodiment 10
A. use CHDM MGE and CHDM DGE and the DGE BPA that contains the oligopolymer component 25/75 weight % blend and polyalkylene polyamine solidifying agent and 2,4,6-three (dimethylamino first Base) the stroke cure time of phenol promotor determines and DSC
Will be from the part (1.9869g, 0.01162 epoxy equivalent (weight)) and 2,4 of the masterbatch of embodiment 7 part A, (0.1135g 5phr) merges and thoroughly mixes so that homogeneous solution to be provided 6-three (dimethylaminomethyl) phenol.Triethylenetetramine (TETA) solidifying agent (0.2836g, 0.01162 amine hydrogen eq) added and thoroughly be mixed into preparation.The Triethylenetetramine (TETA) solidifying agent is described among the embodiment 3 part B.Use the method for embodiment 8 part A to determine the stroke cure time.The 10.3mg of use preparation and the dsc analysis that 11.1mg partly finishes characterize heat release and solidify.The results are given in the table of embodiment 10 ends.
B. use CHDM MGE and CHDM DGE and the DGE BPA that contains the oligopolymer component 25/75 weight % blend and polyalkylene polyamine solidifying agent and 2,4-xylenol promotor The stroke cure time determine and DSC
Will be from the part (2.2345g, 0.0131 epoxy equivalent (weight)) and 2 of the masterbatch of embodiment 7 part A, (0.1277g 5phr) merges and thoroughly mixes so that homogeneous solution to be provided the 4-xylenol.Triethylenetetramine (TETA) solidifying agent (0.3189g, 0.0131 amine hydrogen eq) added and thoroughly be mixed into preparation.The Triethylenetetramine (TETA) solidifying agent is described among the embodiment 3 part B.Use the method for embodiment 8 part A to determine the stroke cure time.The 10.3mg of use preparation and the dsc analysis that 10.7mg partly finishes characterize heat release and solidify.The results are given in the table of embodiment 10 ends.
C. use CHDM MGE and CHDM DGE and the DGE BPA that contains the oligopolymer component 25/75 weight % blend and polyalkylene polyamine solidifying agent and tosic acid monohydrate short Advancing the stroke cure time of agent determines and DSC
Will (0.1161g 5phr) merges and thoroughly mixes so that suspension to be provided with the tosic acid monohydrate from the part (2.0315g, 0.0119 epoxy equivalent (weight)) of the masterbatch of embodiment 7 part A.Triethylenetetramine (TETA) solidifying agent (0.2899g, 0.0119 amine hydrogen eq) added and thoroughly be mixed into preparation.The Triethylenetetramine (TETA) solidifying agent is described among the embodiment 3 part B.Use the method for embodiment 8 part A to determine the stroke cure time.The 9.9mg of use preparation and the dsc analysis that 14.6mg partly finishes characterize heat release and solidify.The results are given in the table of embodiment 10 ends.
D. use cis, the anti-form-1 that contains the oligopolymer component, 3-and 1,4 cyclohexane dimethanol list and two 25/75 w/w % blend of the diglycidylether of glycidyl ether and dihydroxyphenyl propane and poly-inferior The stroke cure time of alkyl polyamine solidifying agent and valeric acid promotor is determined and DSC
Will (0.1322g 5phr) merges and thoroughly mixes so that homogeneous solution to be provided with valeric acid from the part (2.3130g, 0.0135 epoxy equivalent (weight)) of the masterbatch of embodiment 7 part A.Triethylenetetramine (TETA) solidifying agent (0.3301g, 0.0135 amine hydrogen eq) added and thoroughly be mixed into preparation.Described solidifying agent is described among the embodiment 3 part B.Use the method for embodiment 8 part A to determine the stroke cure time.The 9.6mg of use preparation and the dsc analysis that 12.4mg partly finishes characterize heat release and solidify.The results are given in the following table.
a66.19 with 66.49 ℃ mean value, b96.72 with 97.58 ℃ mean value, c573.0 with the mean value of 573.0 joules/g,
d49.29 with 51.12 ℃ mean value, e87.11 with 87.47 ℃ mean value, f530.8 with the mean value of 551.9 joules/g,
g54.09 with 52.12 ℃ mean value, h89.54 with 89.62 ℃ mean value, i707.5 with the mean value of 482.9 joules/g,
j49.37 with 51.22 ℃ mean value, k88.99 with 90.00 ℃ mean value, l517.6 and the mean value of 526.6 joules/g
When the diglycidylether of comparison test I-use dihydroxyphenyl propane and the stroke cure of polyalkylene polyamine solidifying agent Between determine
The part of the DGE BPA that will describe in embodiment 7 part A (1.9579g, 0.01064 epoxy equivalent (weight)) merges with Triethylenetetramine (TETA) solidifying agent (0.2596g, 0.01064 amine hydrogen eq).The solidifying agent that uses is described among the embodiment 3.Use the method for embodiment 8 part A to determine the stroke cure time.Obtain 2.592min+/-stroke cure time of 0.0216min.
Embodiment 11-contains the preparation of the blend of the CHDM DGE of oligopolymer component and DGE BPA Characterize with viscosity
Contain by mixing that DGE BPA prepares a series of blends described in the CHDM DGE of oligopolymer component and the embodiment 1 part B.The GC that contains the CHDM DGE of oligopolymer component analyzes and has disclosed 95.8 area %CHDM DGE (for 4 kinds of independent isomer, 24.39,32.61,12.42, with 26.38 area %), 3.7 area % oligopolymer (＞46 kinds of a small amount of components), surplus is several small amount of impurities.Titration shows 27.74% epoxide (155.13EEW).Viscosity (25 ℃) average out to 86cp.Prepare blend by following method: mix 0.200g (10 weight %) respectively, 0.500g (25 weight %), or the CHDM DGE and the 1.800g that contain the oligopolymer component of 1.000g (50 weight %), the DGE BPA of 1.500g or 1.000g.Measure following viscosity (25 ℃) for blend:
Figure BPA00001257566000481
Embodiment 12-contain the CHDM MGE of oligopolymer component and CHDM DGE mixture (by The preparation of the coupling of Louis acid catalysis and epoxidation reaction) with preparation and the table of the blend of DGE BPA Levy
Prepare Resins, epoxy by following method: the coupling of the epihalohydrin of Louis acid catalysis (epi) and CHDM, in linked reaction, use tin chloride (IV), then be epoxidation reaction.GC analyzes to have disclosed and has the unreacted CHDM of 0.06 area %, 4.19 area %CHDM MGE, and 58.73 area %CHDM DGE, 36.79 area % oligopolymer, surplus is several a small amount of components.Analyze ion and hydrolyzable and total muriate, providing does not have detectable hydrolyzable chlorination thing, does not have detectable ion muriate and 3.52% total muriate.The titration of the aliquot sample of product shows 27.42% epoxide (156.93EEW).2 parts of independent aliquot sample determining product at the I.C.I. cone-and-plate viscometer are 25 ℃ viscosity, and it provides the mean value of 65cp and 66cp respectively.Be 23.097% epoxide (186.30EEW) by titrimetry commercial grade DGE BPA.The kinematic viscosity of DGE BPA is 9659cSt (25 ℃).Use the ASTM D445-06 standard method of test (and calculating of dynamic viscosity) of the kinematic viscosity that is used for transparent and opaque liq.Use these components, preparation blend and measurement kinematic viscosity are as follows:
Figure BPA00001257566000482
aObserved value, bExtrapolated value, cThe I.C.I. cone-plate viscosity of measuring
It will be apparent to those skilled in the art that under the situation that does not depart from scope of the present invention, can in above-mentioned composition and method, carry out some variation.Therefore be intended to all events disclosed herein are interpreted as only be exemplary and the scope of limit request protection not.In addition, the compositions and methods of the invention form that is not subjected to the specific embodiment of above elaboration to comprise that they are mentioned is limit.But the form that these embodiment and they are mentioned is the example to the compositions and methods of the invention.

Claims (12)

1. Resins, epoxy reactive diluent composition, it comprises epoxy resin diluent (A) and resin compound (B), wherein said epoxy resin diluent (A) comprises cis, anti-form-1,3-and-1,4-hexanaphthene dimethyl ether part, and described resin compound (B) comprises the Resins, epoxy that one or more are different from described epoxy resin diluent (A).
2. composition according to claim 1, wherein based on the gross weight of described composition, described composition comprises the described epoxy resin diluent (A) of 0.5 weight % to 99 weight %.
3. composition according to claim 1, wherein said epoxy resin diluent (A) comprises:
(i) cis-1, the diglycidylether of 3-cyclohexanedimethanol; Anti-form-1, the diglycidylether of 3-cyclohexanedimethanol; Cis-1, the diglycidylether of 2-cyclohexanedimethanol; And anti-form-1, the diglycidylether of 4-cyclohexanedimethanol;
(ii) cis-1, the diglycidylether of 3-cyclohexanedimethanol; Anti-form-1, the diglycidylether of 3-cyclohexanedimethanol; The diglycidylether of cis-1,4 cyclohexane dimethanol; Anti-form-1, the diglycidylether of 4-cyclohexanedimethanol; With their any oligopolymer;
(iii) cis-1, the diglycidylether of 3-cyclohexanedimethanol; Anti-form-1, the diglycidylether of 3-cyclohexanedimethanol; The diglycidylether of cis-1,4 cyclohexane dimethanol; Anti-form-1, the diglycidylether of 4-cyclohexanedimethanol; Cis-1, the monoglycidyl ether of 3-cyclohexanedimethanol; Anti-form-1, the monoglycidyl ether of 3-cyclohexanedimethanol; The monoglycidyl ether of cis-1,4 cyclohexane dimethanol; And anti-form-1, the monoglycidyl ether of 4-cyclohexanedimethanol; Or
(iv) cis-1, the diglycidylether of 3-cyclohexanedimethanol; Anti-form-1, the diglycidylether of 3-cyclohexanedimethanol; The diglycidylether of cis-1,4 cyclohexane dimethanol; Anti-form-1, the diglycidylether of 4-cyclohexanedimethanol; Cis-1, the monoglycidyl ether of 3-cyclohexanedimethanol; Anti-form-1, the monoglycidyl ether of 3-cyclohexanedimethanol; The monoglycidyl ether of cis-1,4 cyclohexane dimethanol; Anti-form-1, the monoglycidyl ether of 4-cyclohexanedimethanol; With their any oligopolymer.
4. composition according to claim 3, wherein based on the gross weight of epoxy resin diluent (A), described epoxy resin diluent (A) comprises the described cis-1 of manipulated variable, the monoglycidyl ether of 3-cyclohexanedimethanol; Anti-form-1, the monoglycidyl ether of 3-cyclohexanedimethanol; The monoglycidyl ether of cis-1,4 cyclohexane dimethanol; And anti-form-1, the monoglycidyl ether of 4-cyclohexanedimethanol: and wherein said epoxy resin diluent (A) comprises the described cis-1 of 0.1 weight % to 90 weight %, the monoglycidyl ether of 3-cyclohexanedimethanol; Anti-form-1, the monoglycidyl ether of 3-cyclohexanedimethanol; The monoglycidyl ether of cis-1,4 cyclohexane dimethanol; And anti-form-1, the monoglycidyl ether of 4-cyclohexanedimethanol.
5. curable epoxy resin composition, described curable epoxy resin composition comprise (a) Resins, epoxy reactive diluent composition and (b) blend of at least a solidifying agent and/or at least a curing catalysts; Wherein said Resins, epoxy reactive diluent composition comprises epoxy resin diluent (A) and resin compound (B); And wherein said epoxy resin diluent (A) comprises cis, anti-form-1,3-and-1, and 4-hexanaphthene dimethyl ether part, and described resin compound (B) comprises the Resins, epoxy that one or more are different from described epoxy resin diluent (A).
6. composition according to claim 5, wherein said solidifying agent comprises the material that each molecule has at least one hydrogen atoms, and described Resins, epoxy reactive diluent composition comprises at least one epoxy group(ing), and the described hydrogen atoms in the described solidifying agent have with described Resins, epoxy reactive diluent composition in the reactivity of described epoxy group(ing); And the ratio of the equivalents of the epoxy group(ing) in the equivalents of the hydrogen atoms in the wherein said solidifying agent and the described curable epoxy resin composition is 0.80: 1 to 1.50: 1.
7. composition according to claim 5, described composition also comprises at least a additive; And wherein said additive comprises at least a in following: curing catalyst, and solvent is different from the thinner of described epoxy resin diluent (A), filler, pigment, dyestuff, flow ability modifying agent, thickening material, toughener, releasing agent, wetting agent, stablizer, fire retardant, tensio-active agent and their any combination.
8. composition according to claim 7, the wherein said thinner that is different from described epoxy resin diluent (A) comprises non-reactive diluent, monoepoxide diluents, except comprising cis, anti-form-1,3-and-1, nominal bifunctional epoxy resin thinner beyond bifunctional epoxy resin's thinner of 4-hexanaphthene dimethyl ether part, at least a in reactive non-epoxide diluents and their any combination.
9. one kind comprises the method for solidifying curable epoxy resin composition according to claim 5.
10. method according to claim 9, wherein said method comprise that partly solidified described curable epoxy resin composition to form the second stage product, solidifies described second stage product in the time after a while subsequently fully.
11. cured epoxy resin by method preparation according to claim 9.
12. goods, described goods comprise cured epoxy resin according to claim 11; And wherein said goods are coating, electricity or structural laminated body, and electricity or structure complex body, long filament twine body, moulding bodies, at least a in foundry goods and the package.
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Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110054056A1 (en) * 2008-05-22 2011-03-03 Hefner Jr Robert E Thermoset polyurethanes
WO2012050688A2 (en) 2010-09-30 2012-04-19 Dow Global Technologies Llc Epoxy resin adducts and thermosets thereof
EP2621994A1 (en) 2010-09-30 2013-08-07 Dow Global Technologies LLC Epoxy resin compositions
BR112013007037A2 (en) 2010-09-30 2019-09-24 Dow Global Technologies Llc thermosetting resin composition, partially cured product, fully cured thermoset product, process for preparing a thermosetting composition, process for curing a mixture composition and article
WO2012044455A1 (en) 2010-09-30 2012-04-05 Dow Global Technologies Llc Coating compositions
US8962792B2 (en) 2010-09-30 2015-02-24 Dow Global Technologies Llc Process for preparing epoxy resins
US9321880B2 (en) * 2012-11-13 2016-04-26 Dow Global Technologies Llc Epoxy resin system containing polyethylene tetramines and triethylene diamine catalyst for resin transfer molding processes
WO2014078219A1 (en) * 2012-11-13 2014-05-22 Dow Global Technologies Llc Epoxy resin system containing polyethylene tetraamines for resin transfer molding processes
DK2931822T3 (en) 2012-12-14 2021-09-13 Blue Cube Ip Llc EPOXYCOATINGS WITH HIGH SOLID CONTENT
CN103665325A (en) * 2013-11-25 2014-03-26 苏州宏泉高压电容器有限公司 Epoxy resin and preparation method thereof
US9382472B2 (en) * 2013-12-18 2016-07-05 Rohm And Haas Electronic Materials Llc Transformative wavelength conversion medium
US9464224B2 (en) 2013-12-18 2016-10-11 Rohm And Haas Electronic Materials Llc Transformative wavelength conversion medium
JP6306419B2 (en) * 2014-04-28 2018-04-04 株式会社クラレ Monoglycidyl ether compound and monoallyl ether compound
JP2015209516A (en) * 2014-04-28 2015-11-24 株式会社クラレ Curable composition, and cured product
CN107743503B (en) * 2015-06-25 2020-03-31 陶氏环球技术有限责任公司 Novel epoxy resin system for manufacturing carbon fiber composite material
US10934151B2 (en) 2017-07-28 2021-03-02 Swimc Llc Tinting water-borne and solvent-borne paints and stains with water-only colorants
US10933389B2 (en) * 2017-07-28 2021-03-02 Swimc Llc Tinting water-borne and solvent-borne paints and stains with powdered colorants
EP3702389B1 (en) * 2017-10-24 2024-02-07 Toray Industries, Inc. Epoxy resin composition, prepreg, and fiber-reinforced composite material
AU2018388985B2 (en) * 2017-12-21 2024-03-14 Huntsman Advanced Materials Americas Llc Curable epoxy system
AT521316A1 (en) * 2018-06-07 2019-12-15 All Bones Gmbh Polymer mixture and its use in 3D printing
CN110819202A (en) * 2018-08-07 2020-02-21 广东万爱建筑科技有限公司 Graphene coating applied to building aluminum template release-free agent
US10822517B2 (en) * 2018-11-28 2020-11-03 Industrial Technology Research Institute Resin composition and cured resin composition
WO2021092074A1 (en) * 2019-11-05 2021-05-14 Cambium Biomaterials, Inc. Composition and method for manufacturing resins

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4497764A (en) * 1982-09-30 1985-02-05 Exxon Research & Engineering Co. Epoxy resin compositions of enhanced creep resistance
CN1747979A (en) * 2003-02-03 2006-03-15 Ppg工业俄亥俄公司 Solvent borne 2k coating compositions.

Family Cites Families (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4548961A (en) * 1982-09-30 1985-10-22 Exxon Research & Engineering Co. Epoxy resin compositions of enhanced creep resistance
US4578453A (en) 1984-11-23 1986-03-25 Eastman Kodak Company High molecular weight polyesters
US4623701A (en) 1985-07-10 1986-11-18 The Dow Chemical Company Multifunctional epoxy resins
US5073595A (en) * 1987-12-23 1991-12-17 Minnesota Mining And Manufacturing Company Epoxide resin compositions and method
US5239406A (en) * 1988-02-12 1993-08-24 Donnelly Corporation Near-infrared reflecting, ultraviolet protected, safety protected, electrochromic vehicular glazing
US5355245A (en) * 1988-02-12 1994-10-11 Donnelly Corporation Ultraviolet protected electrochemichromic rearview mirror
US4885319A (en) * 1988-02-29 1989-12-05 Gaf Corporation Solvent resistant irradiation curable coatings
US5463091A (en) 1989-01-17 1995-10-31 The Dow Chemical Company Diglycidyl ether of 4,4'-dihydroxy-α-methylstilbene
JPH0459878A (en) * 1990-06-28 1992-02-26 Nippon Paint Co Ltd Powder coating composition
US5354797A (en) * 1992-08-31 1994-10-11 E. I. Du Pont De Nemours And Company Coating composition of hydroxy functional acrylic polymer, polyol and polyisocyanate crosslinking agent
EP0676431B1 (en) * 1994-04-06 2001-10-10 PPG Industries Ohio, Inc. Coating compositions comprising 1,4-cyclohexane dimethanol
US5681907A (en) * 1996-01-04 1997-10-28 Air Products And Chemicals, Inc. Fast cure amines for ambient and subambient cure of epoxy resins comprising methylamine adducts
US6733880B2 (en) * 2000-01-19 2004-05-11 Hitachi Chemical Co., Ltd. Adhesive film for semiconductor, lead frame with adhesive film for semiconductor and semiconductor device using the same
DE10002605C2 (en) 2000-01-21 2002-06-20 Hilti Ag Curable two-component mortar and its use
JP3681978B2 (en) * 2000-12-19 2005-08-10 株式会社巴川製紙所 Light reflector and reflection type liquid crystal display device
US6548175B2 (en) * 2001-01-11 2003-04-15 International Business Machines Corporation Epoxy-siloxanes based electrically conductive adhesives for semiconductor assembly and process for use thereof
NZ560886A (en) * 2001-12-28 2009-03-31 Illinois Tool Works Adhesive of epoxy compound, aliphatic amine and tertiary amine
TWI223736B (en) * 2002-12-19 2004-11-11 Ind Tech Res Inst Hybrid photoresist with multi reaction models and process for forming pattern using the same
DE10317646A1 (en) * 2003-04-17 2004-11-04 Cognis Deutschland Gmbh & Co. Kg Radiation-curable compositions
US6818293B1 (en) * 2003-04-24 2004-11-16 Eastman Chemical Company Stabilized polyester fibers and films
WO2005088357A1 (en) * 2004-03-16 2005-09-22 Tomoegawa Co., Ltd. Anisotropic diffusing medium and production method therefor
WO2006029140A1 (en) * 2004-09-03 2006-03-16 Dow Global Technologies Inc. Emulsifiable polyisocyanate
JP4135940B2 (en) * 2004-10-20 2008-08-20 株式会社巴川製紙所 Anisotropic diffusion media
US7560821B2 (en) * 2005-03-24 2009-07-14 Sumitomo Bakelite Company, Ltd Area mount type semiconductor device, and die bonding resin composition and encapsulating resin composition used for the same
US7425594B2 (en) * 2005-11-23 2008-09-16 Ppg Industries Ohio, Inc. Copolymer of glycidyl ester and/or ether with polyol
JP5027161B2 (en) * 2006-02-03 2012-09-19 ダウ グローバル テクノロジーズ エルエルシー 1,3 / 1,4-cyclohexanedimethanol monomers and polymers
US20110039982A1 (en) 2008-05-22 2011-02-17 Hefner Jr Robert E Epoxy resins and processes for preparing the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4497764A (en) * 1982-09-30 1985-02-05 Exxon Research & Engineering Co. Epoxy resin compositions of enhanced creep resistance
CN1747979A (en) * 2003-02-03 2006-03-15 Ppg工业俄亥俄公司 Solvent borne 2k coating compositions.

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TW201002780A (en) 2010-01-16
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US8318834B2 (en) 2012-11-27

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